研究者詳細 - 忍久保　洋

PubMed

その他リンク： https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202404194

Diradical character view of energy stabilization in π-stacked dimers of antiaromatic molecules 査読有り国際誌 Open Access

Sugimori, R; Kishi, R; Shinokubo, H; Kitagawa, Y

CHEMISTRY LETTERS 53 巻 ( 12 ) 頁： upae224 2024年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry Letters

We theoretically examined the energy stabilization mechanism of closely π-stacked dimers of antiaromatic molecules from the viewpoint of diradical character (y). Quantum chemical calculations for π-stacked dimer models of cyclobutadienes and Ni(II) norcorroles revealed that the balance between the destabilization due to structural deformation in each monomer and the stabilization due to intermolecular orbital interaction between 4nπ systems and dispersion force determined the stabilization in the π-dimer structures.

DOI： 10.1093/chemle/upae224

その他リンク： https://doi.org/10.1093/chemle/upae224

Catalytic Construction of Stereogenic Boron Center on BODIPY via Enantioselective Suzuki–Miyaura Coupling 査読有り国際誌

Aiko Kondo, Hideaki Takano, Hiroshi Shinokubo

Chemistry Letters 2024年11月

Bowl-Shaped Anthracene-Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion 査読有り国際誌

Wang, KS; Ghosh, A; Shimizu, D; Takano, H; Ishida, M; Kishi, R; Shinokubo, H

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 64 巻 ( 7 ) 頁： e202419289 2024年11月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

The synthesis of bowl-shaped antiaromatic molecules is challenging because the molecular distortion further destabilizes these already inherently reactive molecules. Here, we report the synthesis and properties of bowl-shaped fused anthrylnorcorroles that exhibit near-infrared (NIR) absorption reaching 1900 nm. The oxidation of meso-anthryldibromodipyrrin provides fused anthryldibromodipyrrin, which was converted to the fused mono- and bisanthrylnorcorroles through Ni(0)-mediated intramolecular coupling with a bis(dibromodipyrrin) Ni(II) complex. Single-crystal X-ray diffraction analyses revealed bowl-shaped structures for the fused mono- and bisanthrylnorcorroles, which enables them to act as suitable receptors for C60 with bonding constants of 2.89×103 M−1 and 1.59×103 M−1, respectively. The formation of a 1 : 1 complex between the fused monoanthrylnorcorrole and C60 was confirmed by single-crystal X-ray diffraction analysis. The effective expansion of the π-conjugation through the triple fusion of the norcorrole with the anthracene units substantially enhances the near-infrared absorption bands, which endows these anthrylnorcorroles with effective photothermal conversion.

DOI： 10.1002/anie.202419289

その他リンク： https://onlinelibrary.wiley.com/doi/10.1002/anie.202419289

Zig-zag-fused π-extended BODIPYs via gold-catalysed cycloisomerisation 招待有り査読有り国際誌

Ohashi, F; Takano, H; Shinokubo, H

Chemical Communications 60 巻 ( 88 ) 頁： 12892 - 12895 2024年11月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

π-Extension of the BODIPY core is an effective strategy to modulate the physical properties of BODIPYs. However, π-extension on the zig-zag edge of BODIPYs remains unexplored. Here, we disclose the synthesis of zig-zag-fused BODIPYs through gold-catalysed cycloisomerisation. The obtained BODIPYs show fascinating photophysical properties including near-infrared absorption and emission.

DOI： 10.1039/d4cc04416a

Synthesis and electron-transporting properties of phenazine bisimides 査読有り国際誌

Tajima, K; Moribe, T; Matsuo, K; Yamada, H; Seki, S; Yokokura, S; Shimada, T; Fukui, N; Shinokubo, H

JOURNAL OF MATERIALS CHEMISTRY C 13 巻 ( 2 ) 頁： 655 - 662 2024年10月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Materials Chemistry C

The dual incorporation of imide substituents and imine-type nitrogen atoms into π-systems represents an emerging guideline for the design of robust and high-performance n-type semiconductors. Herein, we have adapted this strategy to a simple molecular motif: anthracene, and thus synthesized phenazine bisimides (PzBIs). PzBIs exhibit superior electron affinity compared to anthracene bisimide and phenazine due to the presence of two types of functional electron-withdrawing units. The existence of imine-type nitrogen atoms in PzBI leads to the formation of two-dimensionally extended brickwork arrangements while anthracene bisimide forms one-dimensionally slipped-stacked arrays. Consequently, the electron mobility of the vacuum-deposited film of N,N′-dicyclohexyl PzBI is ten times higher than that of the corresponding anthracene bisimide. Furthermore, the OFET device of N,N′-bisheptafluorobutyl PzBI exhibits good air persistency, and its intrinsic electron mobility has been estimated to be approximately 0.7 cm2 V−1 s−1 by the time-resolved microwave conductivity measurement. The current study demonstrates that the dual incorporation strategy endows even a simple and small π-system with good performance as an n-type semiconductor.

DOI： 10.1039/d4tc03306j

Synthesis of four regioisomeric Ni(II) azacorroles via oxidative ring-expansion of prefunctionalised norcorroles 査読有り国際共著国際誌

Li, S; Zhang, SW; Ohtake, K; Shinokubo, H; Li, XF

ORGANIC CHEMISTRY FRONTIERS 11 巻 ( 20 ) 頁： 5928 - 5937 2024年10月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Chemistry Frontiers

We explored the synthesis of four regioisomeric formylated and brominated azacorroles via oxidative insertion of prefunctionalised Ni(ii) norcorroles. We also found that the reaction of Ni(ii) azacorroles with the Vilsmeier reagent afforded 2- and 3-formylazacorroles. The structures of all the products were characterised thoroughly by high-resolution mass spectrometry, NMR and UV-vis absorption spectroscopy together with X-ray diffraction analysis. The synthesis of four regioisomers of formyl- and bromoazacorroles allowed a detailed study of the substituent effect depending on the position of the functionality.

DOI： 10.1039/d4qo01415d

Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons 査読有り国際共著国際誌

Yoshina, R; Hirano, J; Nishimoto, E; Sakamoto, Y; Tajima, K; Minabe, S; Uyanik, M; Ishihara, K; Ikai, T; Yashima, E; Omine, T; Ishiwari, F; Saeki, A; Kim, J; Oh, J; Kim, D; Liu, GT; Yasuda, T; Shinokubo, H; Fukui, N

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 43 ) 頁： 29383 - 29390 2024年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral D2-symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., dibenzo[g,p]chrysene (DBC), catalytically affords a figure-eight electron-accepting macrocycle, i.e., cyclobisbiphenylenecarbonyl (CBBC), with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). This inner-bond-cleavage approach also applies to larger PAHs, affording highly distorted molecular frameworks that comprise two figure-eight subunits. Furthermore, we demonstrate that the peripheral functionalization of CBBC with carbazole afforded donor-acceptor-type emitter, which shows thermally activated delayed fluorescence and emits CPL with a g value of 1.0 × 10-2. This g value is ten times higher than those of previously reported chiral TADF-active emitters for circularly polarized organic light-emitting diodes. These results demonstrate that oxidative inner-bond cleavage is a powerful synthetic strategy for creating innovative materials that incorporate molecules with figure-eight structures.

DOI： 10.1021/jacs.4c07985

An n-type semiconducting diazaporphyrin-based hydrogen-bonded organic framework 査読有り国際誌

Sakurai, T; Tanabe, T; Iguchi, H; Li, ZW; Matsuda, W; Tsutsui, Y; Seki, S; Matsuda, R; Shinokubo, H

CHEMICAL SCIENCE 15 巻 ( 32 ) 頁： 12922 - 12927 2024年8月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Science

Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the meso positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and meso-nitrogen atoms. The thermal and chemical stabilities of the HOF were examined using powder X-ray diffraction analysis, and the charge-carrier mobility was determined to be 2.0 × 10−7 m2 V−1 s−1 using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method. An analogous diazaporphyrin, which does not form a HOF, exhibited mobility that was 20 times lower. The results presented herein highlight the crucial role of hydrogen-bonding networks in achieving conductive pathways that can tolerate thermal perturbation.

DOI： 10.1039/d4sc03455d

その他リンク： https://doi.org/10.1039/D4SC03455D

Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators 招待有り査読有り国際誌

Shafie, SA; Nozawa, R; Takano, H; Shinokubo, H

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY 20 巻頁： 1967 - 1972 2024年8月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Beilstein Journal of Organic Chemistry

Norcorrole is a stable 16π-antiaromatic porphyrinoid that exhibits characteristic reactivities and physical properties. Here, we disclose the reaction of Ni(II) norcorroles with alkyl radicals derived from azo radical initiators. The radical selectively attacked the distal α-position relative to the meso-position to construct a nonaromatic bowl-shaped structure. The photophysical and electrochemical properties of the obtained radical adducts were compared to those of the parent Ni(II) norcorrole. The radical reactivity of Ni(II) norcorroles was investigated by density functional theory (DFT) calculations.

DOI： 10.3762/bjoc.20.172

Ultrafine Spatial Modulation of Diazapyrene-Based Two-Dimensional Conjugated Covalent Organic Frameworks 査読有り国際共著国際誌

Li, ZW; Tsuneyuki, T; Paitandi, RP; Nakazato, T; Odawara, M; Tsutsui, Y; Tanaka, T; Miyake, Y; Shinokubo, H; Takagi, M; Shimazaki, T; Tachikawa, M; Suzuki, K; Kaji, H; Ghosh, S; Seki, S

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 33 ) 頁： 23497 - 23507 2024年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Tailormade bottom-up synthesis of covalent organic frameworks (COFs) from various functional building blocks offer not only tunable topology and pore size but also multidimensional properties. High crystallinity is one of the prerequisites for their structures and associated physicochemical properties. Among different π-conjugated motifs for constructing COFs, pyrene-based tetragonal structures are effective in achieving highly ordered and crystalline states. In the present research, we demonstrated that the substitution of pyrene with 2,7-diazapyrene produces nearly “flat” structures of two-dimensional (2D) COF layers by controlling the torsional angle of linker molecules. Featuring finite pore diameters and excellent thermodynamic stability of ∼500 °C, ordered face-to-face (slipped AA) stacking arrangements were produced. Extended electrical conjugation spanning 2D frames with modest optical bandgaps (Eg) of ∼2.1 eV shows the planar character of diazapyrene-based COFs. The stacking of the conjugated 2D frames with small Eg values is also beneficial for the formation of highly stable conducting pathways in the crystalline state, which was confirmed by the results of the microwave conductivity measurements. Nitrogen centers in diazapyrene units also play a key role as the active sites for proton transfer, and the maximum proton conductivity of σ = 10-2 S cm-1 was achieved along the cocontinuous nanopore structures surrounded by the active sites. Results show that tetragonal COFs based on diazapyrene can be used as a highly crystalline two-dimensional material with special electrical and proton-conducting capabilities.

DOI： 10.1021/jacs.4c07091

Homochiral and Heterochiral Self-Sorting Assemblies of Antiaromatic Ni(II) Norcorrole Dimers 査読有り国際誌

Liu, SY; Li, S; Ukai, S; Nozawa, R; Fukui, N; Sugimori, R; Kishi, R; Shinokubo, H

CHEMISTRY-A EUROPEAN JOURNAL 30 巻 ( 39 ) 頁： e202400292 2024年7月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

Recently, π–π stacked antiaromatic π-systems have received considerable attention because they can exhibit stacked-ring aromaticity due to substantial intermolecular orbital interactions. Here, we report three antiaromatic norcorrole dimers that self-assemble to form supramolecular architectures through chiral self-sorting. A 2,2’-linked norcorrole dimer with 3,5-di-tert-butylphenyl groups forms a π-stacked dimer both in solid and solution states via homochiral self-sorting. Its association constant in solution is (3.6±1.7)×105 M−1 at 20 °C. In the solid state, 3,3’-linked norcorrole dimers with 3,5-di-tert-butylphenyl and phenyl groups afford macrocyclic and helical supramolecular assemblies via heterochiral and homochiral self-sorting, respectively. Notably, the subtle modification in the substituent resulted in a complete change in the structure of the aggregates and the chiral self-sorting mode. The present findings demonstrate that structural manipulation in antiaromatic monomer units leads to the formation of various supramolecular assemblies on the basis of the attractive interactions between antiaromatic π-systems.

DOI： 10.1002/chem.202400292

Synthesis of sterically congested double helicene by alkyne cycloisomerization 招待有り査読有り国際誌

Hirano, J; Miyoshi, S; Yashima, E; Ikai, T; Shinokubo, H; Fukui, N

CHEMICAL COMMUNICATIONS 60 巻 ( 47 ) 頁： 6035 - 6038 2024年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

Alkyne cycloisomerization of 2,7,10,15-tetra(ortho-alkynylphenyl)benzo[g,p]chrysene containing bulky 4-alkoxy-2,6-dimethylphenyl groups at the alkyne terminals selectively proceeded at the sterically crowded bay-region. The obtained double helicene adopts a distorted structure with a high racemization barrier due to the intramolecular steric repulsion.

DOI： 10.1039/d4cc01573h

End-to-End Bent Perylene Bisimide Cyclophanes by Double Sulfur Extrusion 査読有り国際誌

Tanaka, Y; Tajima, K; Kusumoto, R; Kobori, Y; Fukui, N; Shinokubo, H

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 23 ) 頁： 16332 - 16339 2024年5月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Bending inherently planar π-cores consisting of only six-membered rings has traditionally been challenging because a powerful transformation is required to compensate for the significant strain energy associated with bending. Herein, we demonstrate that sulfur extrusion can achieve substantial molecular bending of a perylene structure to form a substructure of a Vögtle belt, a proposed yet hitherto elusive carbon nanotube fragment. Bent perylene bisimide (PBI) derivatives were synthesized through a double-sulfur-extrusion reaction from the corresponding sulfur-containing V-shaped precursors with an internal alkyl tether. The effect of bending the inherently planar PBI core, which is a recent topic of interest for the design of advanced organic electronic and optoelectronic materials, was investigated systematically. Increasing the curvature leads to a red shift in the absorption and emission spectra, while the fluorescence quantum yields remain high. This stands in contrast with the nonemissive features of previously reported nonplanar PBI derivatives based on conjugative tethers. Detailed photophysical measurements indicated that the increasing curvature with shorter alkyl tethers (i) slightly facilitates intersystem crossing and (ii) significantly suppresses the internal conversion in the excited state of the present bent PBI derivatives. The latter characteristics originate from the restricted dynamic motion associated with the charge-transfer (CT) character between the core chromophores and the N-aryl units.

DOI： 10.1021/jacs.4c05358

その他リンク： https://doi.org/10.1021/jacs.4c05358

Norcorroles as antiaromatic π-electronic systems that form dimension-controlled assemblies 査読有り国際誌

Ishikawa, S; Yamasumi, K; Sugiura, S; Sato, S; Watanabe, G; Koo, YH; Seki, S; Bando, Y; Haketa, Y; Shinokubo, H; Maeda, H

CHEMICAL SCIENCE 15 巻 ( 20 ) 頁： 7603 - 7609 2024年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Royal Society of Chemistry (RSC)

<jats:p>Norcorroles with 3,4,5-trialkoxyphenyl moieties were synthesized to form thermotropic liquid crystals (LCs), in which triple-decker stacking structures were formed. The LC state exhibited discotic columnar structures to exhibit high electric conductivity.</jats:p>

DOI： 10.1039/d4sc01633e

Changing aromatic properties through stacking: the face-to-face dimer of Ni(II) bis(pentafluorophenyl)norcorrole 査読有り国際共著国際誌

Wang, Q; Sundholm, D; Gauss, J; Nottoli, T; Lipparini, F; Kino, S; Ukai, S; Fukui, N; Shinokubo, H

PHYSICAL CHEMISTRY CHEMICAL PHYSICS 26 巻 ( 20 ) 頁： 14777 - 14786 2024年5月

担当区分：最終著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Physical Chemistry Chemical Physics

Nuclear magnetic resonance (NMR) shielding constants have been calculated for Ni(ii) bis(pentafluorophenyl)norcorrole and its face-to-face stacked dimer at the Hartree-Fock (HF), second-order Møller-Plesset perturbation theory (MP2), complete-active-space self-consistent-field (CASSCF) levels as well as at density functional theory (DFT) levels using several functionals. The calculated 1H NMR shielding constants agree rather well with the experimental ones. The shielding constants of N and Ni calculated at DFT, HF, and MP2 levels differ from those obtained in the CASSCF calculations due to near-degeneracy effects at the Ni atom. The calculated magnetically induced current densities show that the monomer is antiaromatic, sustaining a strong global paratropic ring current, and the dimer is aromatic, sustaining a strong diatropic ring current. Qualitatively the same current density is obtained at the employed levels of theory. The most accurate ring-current strengths are probably obtained at the MP2 level. The aromatic dimer has a short intermolecular distance of less than 3 Å. The intermolecular interaction changes the nature of the frontier orbitals leading to a formal double bond between the norcorrole macrocycles.

DOI： 10.1039/d4cp00968a

Inner-bond-cleavage approach to figure-eight macrocycles from planar aromatic hydrocarbons 査読有り国際誌

Reiji Yoshina, Junichiro Hirano, Emiko Nishimoto, Yuki Sakamoto, Keita Tajima, Shunsuke Minabe, Muhammet Uyanik, Kazuaki Ishihara, Tomoyuki Ikai, Eiji Yashima, Takuya Omine, Fumitaka Ishiwari, Akinori Saeki, Jinseok Kim, Juwon Oh, Dongho Kim, Guanting Liu, Takuma Yasuda, Hiroshi Shinokubo, Norihito Fukui

Journal of the American Chemical Society 146 巻頁： 29383 - 29390 2024年5月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

<jats:p>Contemporary synthetic strategies in organic chemistry rely heavily on the stepwise formation of bonds between fragments of the target compound (‘bottom-up’ approach). Figure-eight aromatic macrocycles represent a considerable challenge for the bottom-up approach, and the lack of versatile synthetic routes to such macrocycles prevents the use of their distinctive chiral D2-symmetric structures in advanced materials. Herein, we demonstrate the oxidative cleavage of internal double bonds of planar polycyclic aromatic hydrocarbons enables the scalable, catalytic, and enantioselective synthesis of figure-eight macrocycles. These macrocycles, with incorporated carbonyl groups, serve as a chiral electron-acceptor unit to furnish a thermally activated delayed fluorescence material with efficient circularly polarized luminescence. The inner-bond-cleavage approach is thus an effective alternative to the bottom-up approach, proving access to hitherto inaccessible materials.</jats:p>

DOI： 10.26434/chemrxiv-2024-j1xxr

A Triply Linked Porphyrin-Norcorrole Hybrid with Singlet Diradical Character 査読有り国際共著国際誌

Wang, KS; Ito, S; Ren, S; Shimizu, D; Fukui, N; Kishi, R; Liu, Q; Osuka, A; Song, JX; Shinokubo, H

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63 巻 ( 16 ) 頁： e202401233 2024年4月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Norcorrole Ni(II) complexes have recently received considerable attention because they are readily accessible antiaromatic molecules. Their high stability under ambient conditions and ease of synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of meso–meso singly linked porphyrin-norcorrole hybrids and a triply linked porphyrin-norcorrole hybrid. The singly linked and triply linked porphyrin-norcorrole hybrids were fully characterized, including an X-ray structural analysis. Due to their orthogonal conformation, the singly linked hybrids maintain the individual electronic properties of their porphyrin and norcorrole subunits, while the triply linked hybrid shows a significantly smaller electrochemical HOMO–LUMO gap (0.45 eV) than that of Ni(II) dimesitylnorcorrole (1.08 eV). Furthermore, the triply linked hybrid exhibits singlet diradical characteristics, as confirmed by VT NMR, ESR, and SQUID experiments.

DOI： 10.1002/anie.202401233

Close Stacking of Antiaromatic Ni(II) Norcorrole Originating from a Four-Electron Multicentered Bonding Interaction 査読有り国際共著国際誌

Kino, S; Ukai, S; Fukui, N; Haruki, R; Kumai, R; Wang, Q; Horike, S; Phung, QM; Sundholm, D; Shinokubo, H

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 13 ) 頁： 9311 - 9317 2024年3月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

A π-conjugated molecule with one electronic spin often forms a π-stacked dimer through molecular orbital interactions between two unpaired electrons. The bonding is recognized as a multicentered two-electron interaction between the two π-conjugated molecules. Here, we disclose a multicentered bonding interaction between two antiaromatic molecules involving four electrons. We have synthesized an antiaromatic porphyrin analogue, Ni(II) bis(pentafluorophenyl)norcorrole. Its dimer adopts a face-to-face stacked structure with an extremely short stacking distance of 2.97 Å. The close stacking originates from a multicenter four-electron bonding interaction between the two molecules. The bonding electrons were experimentally observed via synchrotron X-ray diffraction analysis and corroborated by theoretical calculations. The intermolecular interaction of the molecular orbitals imparts the stacked dimer with aromatic character that is distinctly different from that of its monomer.

DOI： 10.1021/jacs.4c01142

Interaction strength in molecular junctions consisting of π-stacked antiaromatic molecules 査読有り国際誌

Fujii, S; Tomida, R; Yamane, A; Nabeyama, K; Ohkura, H; Shinokubo, H; Nishino, T

JOURNAL OF MATERIALS CHEMISTRY C 12 巻 ( 5 ) 頁： 1640 - 1643 2024年2月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Royal Society of Chemistry (RSC)

<jats:p>The interaction force was measured as the adhesive force acting between norcorrole molecules anchored to the probe surface and the sample surface. This study reveals substantial interactions in π-stacked antiaromatics at the single-molecule scale.</jats:p>

DOI： 10.1039/d3tc04166b

Excimer Formation Driven by Excited-State Structural Relaxation in a Covalent Aminonaphthalimide Dimer 査読有り国際共著国際誌

Jing, R; Li, Y; Tajima, K; Wan, Y; Fukui, N; Shinokubo, H; Kuang, ZR; Xia, AD

JOURNAL OF PHYSICAL CHEMISTRY LETTERS 15 巻 ( 5 ) 頁： 1469 - 1476 2024年1月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

Strongly coupled excimer formation from interchromophoric charge transfer driven by the ultrafast excited-state structural dynamics of a 5,5′-linked 4-amino-1,8-naphthalimide covalent homodimer was investigated by ultrafast transient spectroscopy and chemical calculations. Theoretical calculations indicate that the structural relaxation associated with the dihedral motion leads to significantly enhanced interchromophoric charge transfer (CT) coupling, which favors the formation of an excimer-like symmetry-broken CT state. The formation and relaxation dynamics of the excimer state in the dimer are identified via ultrafast transient absorption and fluorescence spectroscopy. The structural relaxation following the photoexcitation occurs in tens of picoseconds and stabilizes the dimer to the strongly coupled excimer state. The highly polar solvents further stabilize the excimer state and enhance the CT character, which enable efficient electron and excitation energy transport in covalent molecular aggregates.

DOI： 10.1021/acs.jpclett.3c03337

Synthesis and properties of bay-functionalized 9,9′-bifluorenylidene derivatives 査読有り国際誌

Hirano, J; Shinokubo, H; Fukui, N

CHEMISTRY LETTERS 53 巻 ( 1 ) 頁： upad015 2024年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Oxford University Press (OUP)

<jats:title>Abstract</jats:title> <jats:p>Here, we disclose the effect of substitution at the bay-region of 9,9′-bifluorenylidene on its optical and electrochemical properties. Bay-brominated 9,9′-bifluorenylidene was synthesized by the reductive dimerization of 4,5-dibromofluorenone with triethyl phosphite. The subsequent Suzuki–Miyaura cross-coupling afforded arylated derivatives. X-ray diffraction analysis revealed that the bulky bay-substituents twist the overall structure through the relay of the steric repulsion from the bay-region to the fjord-region. The π-extension at the bay-region with tolyl and 4-dimethylaminophenyl groups increases the electron-donating ability, while the introduction of bromo groups enhances the electron-accepting ability.</jats:p>

DOI： 10.1093/chemle/upad015

その他リンク： https://academic.oup.com/chemlett/article-pdf/53/1/upad015/56961460/upad015.pdf

Syntheses of Thiophene-Thiophene-Linked Corrorin Dimers with Tunable Near-Infrared Absorption and Distinctive Reactivity 査読有り国際共著国際誌

Xu, Y; Zhu, B; Zhang, LF; Baryshnikov, G; Sha, F; Nishimoto, E; Takano, H; Li, CJ; Wu, XY; Ågren, H; Shinokubo, H; Xie, YS; Li, QZ

ORGANIC LETTERS 26 巻 ( 2 ) 頁： 571 - 576 2024年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

Thiahexaphyrinone 1 and thia-dipyrrin-appended corrorin 2 have been synthesized. Surprisingly, further oxidation of compound 2 with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in dichloromethane afforded dimer 3 with two molecules of compound 2 linked at the α-carbon atoms of the thienyl units. Treatment of compound 3 with DDQ in MeOH and SnCl2 in tetrahydrofuran/H2O afforded the dimethoxy-attached dimer 4 and hydrogenated dihydroxy-attached dimer 5, respectively. These results provide the first examples for synthesizing thiophene-linked porphyrinoid dimers with tunable near-infrared absorption and chirality.

DOI： 10.1021/acs.orglett.3c04323

Metallaantiaromaticity of 10-Platinacorrole Complexes 査読有り国際共著国際誌

Miwa, K; Yokota, T; Wang, Q; Sakurai, T; Fliegl, H; Sundholm, D; Shinokubo, H

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 2 ) 頁： 1396 - 1402 2024年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

<jats:p>The aromaticity of cyclic π-conjugated organometallic compounds is known as metallaaromaticity. π-Conjugated metallacycles, such as metallabenzenes and metallapentalenes, have been investigated in order to understand the involvement of the d electrons from the metal center in the π-conjugated systems of the organic ligands. Here, we report the synthesis of Pd(II) 10-platinacorrole complexes with cyclooctadiene (COD) and norbornadiene (NBD) ligands. While the Pd(II) 10-platinacorrole COD complex adopts a distorted structure without showing appreciable antiaromaticity, the corresponding NBD complex exhibits distinct antiaromatic character due to its highly planar conformation. Detailed density-functional-theory (DFT) calculations revealed that two d orbitals are involved in the macrocyclic π-conjugation. We furthermore demonstrated that Craig–Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables the systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals.</jats:p>

DOI： 10.1021/jacs.3c10250

Effect of Internal Substituents on the Properties of Dibenzo[g,p]chrysene 査読有り国際誌

Takeo, Y; Hirano, J; Fukui, N; Shinokubo, H

ORGANIC LETTERS 25 巻 ( 47 ) 頁： 8484 - 8488 2023年11月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

We investigated the chemical and physical properties of internally functionalized dibenzo[g,p]chrysene (DBC) derivatives. These molecules exhibit chiral double-helicene-like structures that are configurationally stable at ambient temperatures. The internal substituents control the conformational change in the excited state, thereby modulating the emission intensity. Notably, the DBC derivative with a methylenedioxy unit undergoes aromatization through elimination of the internal substituent upon photoexcitation, resulting in the formation of DBC.

DOI： 10.1021/acs.orglett.3c03428

Effect of internal oxygen substituents on the properties of bowl-shaped aromatic hydrocarbons 査読有り国際誌

Takeo, Y; Hirano, J; Shimizu, D; Fukui, N; Shinokubo, H

ORGANIC CHEMISTRY FRONTIERS 10 巻頁： 5895 - 5901 2023年10月

Intrinsic Photostability in Dithiolonaphthalimide Achieved by Disulfide Bond-Induced Excited-State Quenching 査読有り国際共著国際誌

Zeming Wang, Rui Jing, Yang Li, Di Song, Yan Wan, Norihito Fukui, Hiroshi Shinokubo, Zhuoran Kuang, Andong Xia

Journal of Physical Chemistry Letters 14 巻 ( 38 ) 頁： 8485 - 8492 2023年9月

Unique solvent effect of water in radical cyclization reaction 査読有り国際誌

Suzuki Sara, Govind Soni Aman, Imamura Kosuke, Yorimitsu Hideki, Shinokubo Hiroshi, Higashi Masahiro, Sato Hirofumi

CHEMICAL PHYSICS LETTERS 826 巻頁： 140641 2023年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Physics Letters

The radical cyclization reaction in the aqueous environment by Yorimitsu et al. is revisited using the RISM-SCF-cSED method, a hybrid of quantum chemistry and statistical mechanics theory for molecular liquids. The difference between the barrier height of the forward reaction from the intermediate E-rot, the cyclization step, and that of the backward reaction is crucial to the reaction yield. Considering the effect of hydrogen bonding through the RISM theory, we found that the barrier height for the forward reaction is lower, especially in water. In other words, considering microscopic solvation effects clearly shows the difference between water and DMSO solvents, explaining the remarkable acceleration of the reaction in the aqueous environment.

DOI： 10.1016/j.cplett.2023.140641

Easily Switchable 18π-, 19π-, and 20π-Conjugation of Diazaporphyrin Double-Pincer Bispalladium Complexes 査読有り国際誌

Sakurai T., Hiraoka Y., Tanaka H., Miyake Y., Fukui N., Shinokubo H.

Angewandte Chemie - International Edition 62 巻 ( 12 ) 頁： e202300437 2023年2月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

NiII 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin serves as a double tridentate ligand to PdII ions to provide a pincer-type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic PdII centers to the meso-nitrogen atoms. We isolated and characterized one- and two-electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two-electron reduction species was confirmed by 1H NMR spectroscopy, UV/Vis-near-IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X-ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state.

DOI： 10.1002/anie.202300437

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202300437

Near-Infrared-Responsive Hydrocarbons Designed by π-Extension of Indeno[1,2,3,4-pgra]perylene at the 1,2,12-Positions 査読有り国際共著国際誌

Kato M., Kim J., Oh J., Shimizu D., Fukui N., Shinokubo H.

Chemistry - A European Journal 2023年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

The relationship between the overall electronic structure of π-conjugated molecules and the arrangement of their constituent elements is of fundamental importance. Establishing rational design guidelines for conjugated hydrocarbons with narrow HOMO-LUMO gaps is useful to develop near-infrared (NIR) responsive dyes and redox-active materials. This study describes the synthesis and properties of three conjugated hydrocarbons, i. e., an indenonaphthoperylene, an indenoterrylene, and a diindenoterrylene. These molecules exhibit NIR absorption despite the absence of significant antiaromaticity and diradical character. Notably, the indenonaphthoperylene exhibits red-to-NIR emission in the 620–850 nm region. The indenoterrylene and the diindenoterrylene exhibit NIR absorption tailing to 870 and 940 nm, respectively. Moreover, the effect of the π-extension of indenoperylene is disclosed in order to propose guidelines for achieving a narrow HOMO-LUMO gap with negligible antiaromaticity and diradical character.

DOI： 10.1002/chem.202300249

Dinaphthooxepine Bisimide Undergoes Oxygen Extrusion Reaction upon Electron Injection at Room Temperature 査読有り国際誌

Odajima Mai, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS 25 巻 ( 1 ) 頁： 282 - 287 2023年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

We report the synthesis and properties of a dinaphthooxepine bisimide (DNOBI), a nonplanar perylene bisimide (PBI) analogue with an inserted oxygen atom. A DNOBI underwent an oxygen-extrusion reaction smoothly upon electron injection at room temperature, affording PBI in good yield. Studies on the reaction mechanism suggest that the injection of two electrons triggers the isomerization of DNOBI to dinaphthooxanorcaradiene bisimide, which is a key step in inducing the oxygen-extrusion reaction.

DOI： 10.1021/acs.orglett.2c04173

One-dimensional stacking array of 10,20-diphenyl-5,15-diazaporphyrin metal complexes 招待有り査読有り国際誌

Mori S., Sakurai T., Nishimura T., Fukui N., Miyake Y., Shinokubo H.

Journal of Porphyrins and Phthalocyanines 27 巻頁： 1035 - 1041 2023年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Porphyrins and Phthalocyanines

We prepared a free-base 10,20-diphenyl-5,15-diazaporphyrin and its Ni(II), Cu(II), Pd(II), and Pt(II) complexes. These molecules uniformly form an infinite one-dimensional p-stacking array in the solid state. The four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent dominate the crystal packing arrangement. The present study revealed that the meso-nitrogen atom of diazaporphyrins would be used as an inherent hydrogen bonding acceptor to construct supramolecular assemblies.

DOI： 10.1142/s1088424622500997

Diazazethrene bisimide: a strongly electron-accepting π-system synthesized via the incorporation of both imide substituents and imine-type nitrogen atoms into zethrene 査読有り国際誌

Tajima K., Matsuo K., Yamada H., Fukui N., Shinokubo H.

Chemical Science 14 巻 ( 3 ) 頁： 635 - 642 2022年12月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Science

The development of highly electron-accepting π-systems is a fundamentally challenging issue despite their potential applications as high-performance n-type organic semiconductors, organic rechargeable batteries, and stable redox-active organocatalysts. Herein, we demonstrate that the incorporation of both imide substituents and imine-type nitrogen atoms into zethrene affords the strongly electron-accepting π-system diazazethrene bisimide (DAZBI). DAZBI has a low-lying LUMO (−4.3 eV vs. vacuum) and is readily reduced by the weak reductant l-ascorbic acid to afford the corresponding dihydro species. The injection of two electrons into DAZBI provides the corresponding dianion. These reduced species display remarkable stability, even under ambient conditions, and an intense red fluorescence. A DAZBI dimer, which was also synthesized, effectively accommodated four electrons upon electron injection.

DOI： 10.1039/d2sc05992d

Highly soluble Ni(II) dithienylnorcorrole 招待有り査読有り国際共著国際誌

Itabuchi Shiori, Nozawa Ryo, Yoshida Takuya, Fukui Norihito, Shinokubo Hiroshi

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 頁： A - E 2022年11月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Porphyrins and Phthalocyanines

Recently, norcorrole Ni(II) complexes have received much attention because they exhibit peculiar solid-state structures and fascinating electronic properties originating from their distinct antiaromatic character. In this work, we have prepared a norcorrole Ni(II) complex with 5-hexylthien-2-yl substituents at the meso-positions, of which the antiaromatic nature was evaluated by 1H NMR analysis as well as NICS and ACID calculations. The X-ray diffraction analysis elucidated its molecular structure and crystal packing arrangement. Crystal packing structures of Ni(II) meso-di(5-methylthien-2-yl)norcorrole and Ni(II) meso-di(5-hexylthien-2-yl)norcorrole were markedly different. The latter provided a polar crystal because of the unidirectional alignment of 5-hexylthien-2-yl groups in the solid state.

DOI： 10.1142/S1088424622500730

Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule 査読有り国際共著国際誌

Liu Si-Yu, Kishida Natsuki, Kim Jinseok, Fukui Norihito, Haruki Rie, Niwa Yasuhiro, Kumai Reiji, Kim Dongho, Yoshizawa Michito, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145 巻 ( 4 ) 頁： 2135 - 2141 2022年10月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Stacked-ring aromaticity arising from the close stacking of antiaromatic π-systems has recently received considerable attention. Here, we realize stacked-ring aromaticity via a rational supramolecular approach. A nanocapsule composed of bent polyaromatic amphiphiles was employed to encapsulate several antiaromatic norcorrole Ni(II) complexes (NCs) in water. The resulting micellar capsules display high stability toward heating and concentration change. The encapsulation resulted in the appearance of a broad absorption band in the near-infrared region, which is characteristic of norcorroles with close face-to-face stacking. Importantly, a meso-isopropyl NC, which does not exhibit π-stacking even in a concentrated solution or the crystalline phase, adopted π-stacking with stacked-ring aromaticity in the supramolecular micellar capsule.

DOI： 10.1021/jacs.2c08795

Planarization of a bowl-shaped molecule by triple-decker stacking 査読有り国際誌

Kawashima Hiroyuki, Fukui Norihito, Phung Quan Manh, Yanai Takeshi, Shinokubo Hiroshi

CELL REPORTS PHYSICAL SCIENCE 3 巻 ( 9 ) 頁： 101045 - 101045 2022年9月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Cell Reports Physical Science

A bowl-shaped π-conjugated molecule typically undergoes bowl-inversion motion via a planarized transition state (TS), the highest-energy state along the reaction coordinate between two minimum bowl structures. Isolation of such planarized state has been challenging. Here, we report that a platinum(II) complex of antiaromatic porphyrin, norcorrole, adopts bowl-shaped conformation in solution but can become planar in solid. In the crystalline state, the norcorrole Pt(II) complex forms triple-decker stacking structures, in which the planarized norcorrole is stabilized and sandwiched between two bowl-shaped norcorroles. The planar conformation corresponds to the TS structure in the dynamic bowl-to-bowl inversion motion of the bowl-shaped molecule. Detailed theoretical studies have revealed that the intrinsically unstable planar conformation is stabilized by the dispersion force among the substituents and enhanced Pt–Pt interactions created by the antiaromatic macrocyclic ligand.

DOI： 10.1016/j.xcrp.2022.101045

d-Mannose-appended 5,15-diazaporphyrin for photodynamic therapy 査読有り国際共著国際誌

Ali Lamiaa M. A., Miyagawa Kazuya, Fukui Norihito, Onofre Melanie, El Cheikh Khaled, Morere Alain, Clement Sebastien, Gary-Bobo Magali, Richeter Sebastien, Shinokubo Hiroshi

ORGANIC & BIOMOLECULAR CHEMISTRY 2022年8月

Gram-Scale Diversity-Oriented Synthesis of Dinaphthothiepine Bisimides as Soluble Precursors for Perylene Bisimides 査読有り国際誌

Tanaka Yuki, Matsuo Kyohei, Yamada Hiroko, Fukui Norihito, Shinokubo Hiroshi

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2022 巻 ( 31 ) 2022年8月

Stepwise N-Methylation of Ruthenium and Cobalt 5,15-Diazaporphyrins: Post-Functionalization of Porphyrinoid Catalysts 査読有り国際誌

Nishijo Mayu, Mori Shiho, Nishimura Tsubasa, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-AN ASIAN JOURNAL 17 巻 ( 14 ) 頁： e202200305 2022年7月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - An Asian Journal

Post-functionalization of porphyrinoid catalysts provides a powerful tool for fine-tuning their electronic structure. We have succeeded in the stepwise methylation of the peripheral nitrogen atoms in ruthenium and cobalt 5,15-diazaporphyrins. The axial coordination of an anion to the metal center accelerates the second methylation through charge neutralization. N-Methylation of the diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity.

DOI： 10.1002/asia.202200305

Protonation-Induced Antiaromaticity in Octaaza[8]circulenes: Cyclooctatetraene Scaffolds Constrained with Four Amidine Moieties 査読有り国際共著国際誌

Akahori Shuhei, Kaga Atsushi, Kim Jinseok, Yorimitsu Hideki, Kim Dongho, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-AN ASIAN JOURNAL 17 巻 ( 12 ) 頁： e202200244 2022年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - An Asian Journal

The switching of cyclic π-conjugation pathways using external stimuli is an attractive research topic in the field of organic chemistry. Here, we synthesized C4h-symmetric octaaza[8]circulenes with four peripherally arranged amidine moieties that exhibit enhanced antiaromaticity upon protonation. Titration experiments with methanesulfonic acid revealed the formation of the tetraprotonated forms of the octaaza[8]circulenes in solution. Single-crystal X-ray diffraction analyses and theoretical calculations indicated that the contribution of the 8π antiaromatic character of the octaaza[8]circulenes is enhanced by the delocalization of charge through the protonation of the pyridine rings.

DOI： 10.1002/asia.202200244

Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer 査読有り国際共著国際誌

Niu Xinmiao, Tajima Keita, Kong Jie, Tao Min, Fukui Norihito, Kuang Zhuoran, Shinokubo Hiroshi, Xia Andong

PHYSICAL CHEMISTRY CHEMICAL PHYSICS 24 巻 ( 22 ) 頁： 14007 - 14015 2022年6月

Synthesis and Tautomerization of 5-Azaporphyrinium Cations 査読有り国際誌

Takiguchi Asahi, Shinokubo Hiroshi

CHEMISTRY LETTERS 51 巻 ( 6 ) 頁： 590 - 593 2022年6月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

Ring closure of 1-oxo-19-(phenylamino)bilin affords 5-azaporphyrinium cations. The introduction of a phenyl group on the meso-nitrogen induces a positive charge in the porphyrinic skeleton. Steric repulsion between the N-phenyl and ¢-ethyl substituents results in the deformation of the inner-cavity to a rectangle. The rectangular cavity and cationic charge induced the unique tautomerization of the inner-NH protons.

DOI： 10.1246/cl.220122

5-Thiaporphyrinium cation: effect of sulphur incorporation on excited state dynamics 査読有り国際共著国際誌

Takiguchi Asahi, Inai Naoto, Kang Seongsoo, Hagai Masaya, Lee Seokwon, Yanai Takeshi, Kim Dongho, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 58 巻 ( 40 ) 頁： 5956 - 5959 2022年5月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

We synthesised thionium-ion embedded aromatic porphyrinoids: a free-base 5-thiaporphyrinium cation and its zinc complex. The sulphur atom effectively participates in the macrocyclic π-conjugation. Fluorescence quantum yields of thiaporphyrinium cations were lower than 1% unlike oxaporphyrinium cations. Detailed photophysical analysis and DFT calculations clarified the vibrational mode regarding the out-of-plane motion of the sulphur atom induced ultrafast quenching of the excited state in comparison to the corresponding oxaporphyrinium cations.

DOI： 10.1039/d2cc00522k

Diverse Crystal Structures of Ion Pairs Consisting of Oxaporphyrinium Cations and Pentacyanocyclopentadienide 査読有り

Asahi Takiguchi, Hiroki Tanaka, Hiromitsu Maeda, Hiroshi Shinokubo

Bulletin of the Chemical Society of Japan 95 巻 ( 5 ) 頁： 796 - 801 2022年3月

Nitrogen Extrusion of Diazacorrphycenes to Azacorroles and Synthesis of Two Types of Copper 10-Azacorrole Complexes 査読有り国際誌

Yagi Atsumi, Okada Naoya, Fukui Norihito, Tanaka Hisaaki, Hatakeyama Takuji, Shinokubo Hiroshi

CHEMISTRY LETTERS 51 巻 ( 3 ) 頁： 321 - 324 2022年3月

Synthesis of Dibenzo[h,t]rubicene through Its Internally Dimethoxy-substituted Precursor 査読有り国際誌

Kato Masaki, Fukui Norihito, Shinokubo Hiroshi

CHEMISTRY LETTERS 51 巻 ( 3 ) 頁： 288 - 291 2022年3月

A Heme-Acquisition Protein Reconstructed with a Cobalt 5-Oxaporphyrinium Cation and Its Growth-Inhibition Activity Toward Multidrug-Resistant Pseudomonas aeruginosa 査読有り国際誌

Takiguchi Asahi, Sakakibara Erika, Sugimoto Hiroshi, Shoji Osami, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61 巻 ( 7 ) 頁： e202112456 2022年2月

Isolation and Structure Analysis of a Ni(II) Norcorrole Radical Anion 査読有り国際誌

Ukai Shusaku, Fukui Norihito, Ikeue Takahisa, Shinokubo Hiroshi

Chemistry Letters 51 巻 ( 2 ) 頁： 182 - 184 2022年2月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：The Chemical Society of Japan

A radical anion of Ni(II) meso-dimesitylnorcorrole was prepared and isolated upon chemical reduction of the corresponding neutral species with cobaltocene (CoIICp2). The radical anion was substantially stable under degassed solution conditions. X-ray crystal analysis of the radical anion revealed that the structural change by one-electron reduction is marginal. DFT calculations demonstrated that the reorganization energy of Ni(II) norcorrole upon one-electron reduction is smaller than those of Zn(II) porphyrin and C60 fullerenes.

DOI： 10.1246/cl.210715

A Supramolecular Polymer Constituted of Antiaromatic Ni(II) Norcorroles 査読有り国際誌

Shusaku Ukai, Aiko Takamatsu, Masaki Nobuoka, Yusuke Tsutsui, Norihito Fukui, Soichiro Ogi, Shu Seki, Shigehiro Yamaguchi, Hiroshi Shinokubo

Angewandte Chemie International Edition 61 巻頁： e202114230 2022年2月

Indeno[1,2,3,4-pqra]Perylene: A Medium-Sized Aromatic Hydrocarbon Exhibiting Full-Range Visible-Light Absorption 査読有り国際誌

Kato, M; Fukui, N; Shinokubo, H

CHEMISTRY-A EUROPEAN JOURNAL 28 巻 ( 2 ) 頁： e202103647 2022年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

We report the synthesis and properties of indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C24H12 that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.

DOI： 10.1002/chem.202103647

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202103647

Dual-Ion NiNc Battery: A Sustainable Revolution for Sodium Organic Batteries 査読有り国際誌

Hwang Jinkwang, Matsumoto Kazuhiko, Hagiwara Rika, Ukai Shusaku, Shinokubo Hiroshi, Shin Ji-Young

BATTERIES & SUPERCAPS 4 巻 ( 10 ) 頁： 1605 - 1610 2021年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Batteries and Supercaps

Dual-ion mobilities of Na organic batteries are investigated with in-situ XRD analysis and computational estimation considering molecular alignments in the solid state, signifying the interactive variations of ionic-pairs of an ionic liquid electrolyte and an antiaromatic molecule, nickel(II) norcorrole (NiNc). An appropriate cavity sphere in three-dimensional molecular alignments dispensed mobilities of dual-ion in an ionic liquid, resulting in high battery capacities, supplemented with the comparison of Mes-NiNc and Ph-NiNc molecular alignments. In-situ XRD experiment, computation, and simulation perspectives afforded prospective insertion and desertion behaviors of cations and anions.

DOI： 10.1002/batt.202100193

Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C-H fluorination 査読有り国際誌

Mori Shiho, Nishimura Tsubasa, Shinokubo Hiroshi, Miyake Yoshihiro

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 25 巻 ( 10N12 ) 頁： 991 - 996 2021年10月

Antiaromatic 1,5-Diaza-s-indacenes 査読有り国際共著国際誌

Hanida Kensuke, Kim Jinseok, Fukui Norihito, Tsutsui Yusuke, Seki Shu, Kim Dongho, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 38 ) 頁： 20765 - 20770 2021年9月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

s-Indacene is a classical non-alternant hydrocarbon that contains 12 π-electrons in a cyclic π-conjugation system. Herein, we report its nitrogen-doped analogue, 1,5-diaza-s-indacene. 1,5-Diaza-s-indacenes were readily prepared from commercially available 2,5-dichlorobenzene-1,4-diamine through a two-step transformation consisting of a palladium-catalyzed Larock cyclization with diaryl acetylenes followed by hydrogen abstraction. The thus obtained 1,5-diaza-s-indacenes exhibited distinct antiaromaticity, as manifested in clear bond-length alternation, a forbidden HOMO–LUMO transition, and a paratropic ring current. As compared to the parent s-indacene, the 1,5-diaza-s-indacenes showed higher electron-accepting ability owing to the presence of imine-type nitrogen atoms. The 1,5-diaza-s-indacene core is effectively conjugated with the peripheral aryl groups, which enables fine-tuning of the absorption spectra and redox properties. The two possible localized forms of 1,5-diaza-s-indacene were compared in terms of their energetic aspects.

DOI： 10.1002/anie.202109003

Synthesis of Tetrasilatetrathia[8]circulenes through C-I and C-H Silylation 招待有り査読有り国際誌

Akahori Shuhei, Fujihara Tetsuaki, Tsuji Yasushi, Shinokubo Hiroshi, Miyake Yoshihiro

SYNTHESIS-STUTTGART 53 巻 ( 17 ) 頁： 2995 - 3000 2021年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Georg Thieme Verlag KG

<jats:title>Abstract</jats:title><jats:p>We have succeeded in the synthesis of various tetrasilatetrathia[8]circulenes with alkyl and aryl groups on the silicon atoms. We also disclosed the effect of phosphine ligands on palladium-catalyzed silylation of tetraiodotetrathienylene and rhodium-catalyzed intramolecular silylation of tetrasilyltetrathienylenes. Experimental and theoretical analysis revealed the effect of the substituents on the silicon atoms on their electronic property.</jats:p>

DOI： 10.1055/a-1437-9917

Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes 査読有り国際共著国際誌

Kawashima Hiroyuki, Ukai Shusaku, Nozawa Ryo, Fukui Norihito, Fitzsimmons Garrett, Kowalczyk Tim, Fliegl Heike, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 143 巻 ( 28 ) 頁： 10676 - 10685 2021年7月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Three-dimensional aromaticity arising from the close stacking of two antiaromatic π-conjugated macrocycles has recently received considerable attention. Here, a cyclophane consisting of two antiaromatic Ni(II) norcorrole units tethered with two flexible alkyl chains was synthesized. The norcorrole cyclophane showed crystal polymorphism providing three different solid-state structures. Surprisingly, one of them adopted an aligned face-to-face stacking arrangement with negligible displacement along the slipping axis. Although the exchange repulsion between two π-clouds should be maximized in this orientation, the π-πdistance is remarkably close (3.258 Å). Three-dimensional aromaticity in this conformation has been supported experimentally and theoretically as evidenced by small bond length alternations as well as the presence of a diatropic ring current. An analogous cyclophane with two aromatic Ni(II) porphyrin units was prepared for comparison. The porphyrin cyclophane exhibited a slipped-stacking conformation with a larger displacement (2.9 Å) and a larger interplanar distance (3.402 Å) without noticeable change of the aromaticity of each porphyrin unit. In solution, the norcorrole cyclophane forms a twist stacking arrangement with effective interplanar orbital overlap and exists in an equilibrium between stacked and nonstacked structures. Thermodynamic parameters of the stacking process were estimated, revealing an inherently large attractive interaction operating between two norcorrole units, which has been further supported by energy decomposition analysis.

DOI： 10.1021/jacs.1c04348

Non-Planar Perylene Bisimide Analogues with Inserted Carbonyl and Methylene Subunits 査読有り国際誌

Odajima Mai, Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 29 ) 頁： 15838 - 15843 2021年7月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

The synthesis and properties of dinaphthotropone bisimide (DNTrBI) and dinaphthocycloheptatriene bisimide (DNCHepBI) are described. Their molecular design is conceptually based on the insertion of a carbon atom into a perylene bisimide (PBI) core. These molecules adopt non-planar structures due to the presence of a seven-membered ring. The PBI derivative into which a carbonyl group was inserted (DNTrBI) immediately underwent nonradiative decay and/or intersystem crossing in its excited state. The PBI derivative into which a methylene group was inserted (DNCHepBI) was susceptible to deprotonation on account of the two electron-withdrawing naphthalene monoimide units. Subsequent aerobic oxidation resulted in the formation of a C−C bond at the central methylene unit, thus affording a σ-dimer. The formation of this C−C bond is dynamically redox-active, i.e., electron injection into the σ-dimer almost quantitatively regenerated the deprotonated DNCHepBI.

DOI： 10.1002/anie.202104882

Acridino[2,1,9,8-klmna]acridine Bisimides: An Electron-Deficient pi-System for Robust Radical Anions and n-Type Organic Semiconductors 査読有り国際誌

Tajima Keita, Matsuo Kyohei, Yamada Hiroko, Seki Shu, Fukui Norihito, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 25 ) 頁： 14060 - 14067 2021年6月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

We report the synthesis and properties of acridino[2,1,9,8-klmna]acridine bisimide (AABI), a nitrogen-doped anthanthrene with two imide functionalities. AABI exhibits excellent electron affinity as evident by its low-lying LUMO level (−4.1 eV vs. vacuum). Single-electron reduction of one AABI derivative afforded the corresponding radical anion, which was stable under ambient conditions. Photoconductivity measurements suggest that the intrinsic electron mobility of an N-phenethyl AABI derivative obeys a band-transport model. Accordingly, an electron mobility of 0.90 cm2 V−1 s−1 was attained with the corresponding single-crystal organic field-effect transistor (OFET) device. The vacuum-deposited OFET device consisting of a polycrystalline sample exhibited high electron mobility of up to 0.27 cm2 V−1 s−1 even in air. This study demonstrates that dual incorporation of both imide substituents and imine-type nitrogen atoms is an effective strategy to create novel electron-deficient π-systems.

DOI： 10.1002/anie.202102708

Synthesis and Characterization of 16 pi Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen 査読有り国際誌

Nakazato Takumi, Takekoshi Haruka, Sakurai Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 25 ) 頁： 13877 - 13881 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

We describe the two-electron reduction of N,N′-dimethyl-2,7-diazapyrenium dications (MDAP2+), which afforded the corresponding reduced form (MDAP0) as a highly electron-rich 16π antiaromatic system. A single-crystal X-ray diffraction analysis of MDAP0 revealed a distorted quinoidal structure with high bond-length alternation. The 1H NMR spectrum of MDAP0 exhibited a diagnostic proton signal (4.6 ppm) that is distinctly upfield shifted compared to that of aromatic diazapyrene (8.3 ppm). Theoretical calculations supported the existence of a paratropic ring current. These results indicate that MDAP0 exhibits antiaromatic character derived from its peripheral 16π-electron conjugation.

DOI： 10.1002/anie.202103667

Quadruply BN-Fused Tetrathia[8]circulenes with Flexible Frameworks: Synthesis, Structures and Properties 査読有り国際誌

Akahori Shuhei, Sasamori Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL 27 巻 ( 31 ) 頁： 8178 - 8184 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

Quadruply BN-fused tetrathia[8]circulenes were synthesized through four-fold electrophilic borylation. The single-crystal X-ray diffraction analysis revealed that the BN-fused tetrathia[8]circulene with peripheral phenyl groups exhibits crystal polymorphism, in which the circulene core adopts both planar and saddle conformations in the solid state. The experimental and theoretical studies revealed that the weaker aromaticity of azaborine compared with benzene renders the flexibility of the BN-fused tetrathia[8]circulenes.

DOI： 10.1002/chem.202100454

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202100454

Iron hexamesityl-5,15-diazaporphyrin: synthesis, structure and catalytic use for direct oxidation of sp(3) C-H bonds 査読有り国際誌

Nishimura Tsubasa, Sakurai Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

DALTON TRANSACTIONS 50 巻 ( 18 ) 頁： 6343 - 6348 2021年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Dalton Transactions

Iron hexamesityl-5,15-diazaporphyrin was synthesized through the cross-coupling reaction of tetrabromodiazaporphyrin. The use of chloroiron(iii) hexamesityl-5,15-diazaporphyrin as a catalyst for oxidation of cyclooctane showed high performance with a total TON up to 731. The introduction of bulky mesityl groups at β-positions prevented the catalyst deactivation via formation of a μ-oxo dimer.

DOI： 10.1039/d1dt00893e

PubMed

Cationic Nickel(II) Pyridinophane Complexes: Synthesis, Structures and Catalytic Activities for C-H Oxidation 査読有り国際誌

Nishimura Tsubasa, Ando Yuki, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY LETTERS 50 巻 ( 5 ) 頁： 1049 - 1052 2021年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

A series of nickel(II) pyridinophane complexes were synthesized and characterized by X-ray crystallographic analysis. Their IR spectra supported the existence of mononuclear nickel(II) complexes in solution. Furthermore, we conducted catalytic C–H oxidation of cyclooctane with nickel(II) pyridinophanes as the catalysts. The activity of nickel(II) pyridinophanes was affected by steric hindrance around the nitrogen atoms.

DOI： 10.1246/cl.210074

Redox-induced reversible [2+2] cycloaddition of an etheno-fused diporphyrin 査読有り国際誌

Miyagawa Kazuya, Hisaki Ichiro, Fukui Norihito, Shinokubo Hiroshi

CHEMICAL SCIENCE 12 巻 ( 14 ) 頁： 5224 - 5229 2021年4月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Science

3,5-Ethenoporphyrin is a π-extended porphyrin containing a fused ethene unit between themeso- and β-positions, exhibiting unique contribution of macrocyclic antiaromaticity. We have recently reported that its analogue, etheno-fused diporphyrin, underwent thermal [2 + 2] cycloaddition to furnish X-shaped cyclobutane-linked tetraporphyrins. Here we demonstrate that the cyclobutane-ring formation is dynamically redox-active. Namely, the tetraporphyrin underwent two-step four-electron oxidation to afford two etheno-fused diporphyrin dications. The reduction of the resulting dication regenerated the cyclobutane-linked tetraporphyrin. The dication was sufficiently stable to allow its isolation under ambient conditions. The structure of the dication has been confirmed by1H NMR spectroscopy and X-ray diffraction analysis. Importantly, the simultaneous double C-C bond cleavage in the cyclopropane ring in the tetraporphyrin is exceptional among dynamic redox (dyrex) systems to achieve large structural changes, thus offering new insights for the design of novel redox-active functional organic materials for electrochromic dyes, organic batteries, and organic memories.

DOI： 10.1039/d1sc00438g

Synthesis and Properties of an 18 pi Aromatic Norcorrole P(V) Complex 査読有り国際誌

Yoshida Takuya, Shafie Siham Asyiqin, Kawashima Hiroyuki, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS 23 巻 ( 7 ) 頁： 2826 - 2830 2021年4月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Publications

[16]Norcorrole is an antiaromatic ring-contracted porphyrinoid. Here, we show that the phosphorus insertion of the free-base [16]norcorrole switches its antiaromaticity to aromaticity. The treatment of a free-base meso-dimesityl[16]norcorrole with phosphorus tribromide in pyridine afforded an [18]norcorrole P(V) complex, which exhibited porphyrin-like absorption and fluorescence spectra. The phosphorus center adopted a distorted tetragonal pyramidal coordination geometry. The distinct aromatic nature of the [18]norcorrole P(V) complex was corroborated both experimentally and theoretically.

DOI： 10.1021/acs.orglett.1c00823

Enthalpically and Entropically Favorable Self-Assembly: Synthesis of C-4h-Symmetric Tetraazatetrathia[8]circulenes by Regioselective Introduction of Pyridine Rings 査読有り

Akahori Shuhei, Sasamori Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL 27 巻頁： 5675 - 5682 2021年3月

Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation 査読有り

Takahiro Sakurai, Takumi Nakazato, Hiroshi Shinokubo, and Yoshihiro Miyake

Organic Letters 23 巻 ( 6 ) 頁： 2099 - 2103 2021年3月

Dinaphtho[1,8-bc:1 ',8 '-fg][1,5]dithiocine Bisimide 招待有り査読有り

Tanaka Yuki, Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ASIAN JOURNAL OF ORGANIC CHEMISTRY 10 巻 ( 3 ) 頁： 541 - 544 2021年2月

Dual Emission of a Free-Base 5-Oxaporphyrinium Cation from its cis- and trans-NH Tautomers 査読有り国際共著

Takiguchi Asahi, Kang Seongsoo, Fukui Norihito, Kim Dongho, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 6 ) 頁： 2915 - 2919 2021年2月

Complexation of 2,7-diazapyrene with boron for structural and electronic tuning 査読有り

Nakazato Takumi, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS 57 巻 ( 3 ) 頁： 327 - 330 2021年1月

Dual-ion charge-discharge behaviors of Na-NiNc and NiNc-NiNc batteries 査読有り国際誌

Hwang Jinkwang, Hagiwara Rika, Shinokubo Hiroshi, Shin Ji-Young

MATERIALS ADVANCES 2 巻 ( 7 ) 頁： 2263 - 2266 2021年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Materials Advances

Dual-ion sodium-organic secondary batteries were produced with anti-aromatic porphyrinoid, NiNc, as an active electrode material, which exhibited inherent charge-discharge behavior with high discharge capacity, high stability, and high Coulombic efficiency at high current density (132.6 mA h g-1 discharge capacity and 99.4% efficiency at the 100th cycle with 1 A g-1 of current density and 95.3 mA h g-1 discharge capacity and 99.3% efficiency at the 100th cycle with 2 A g-1 of current density).

DOI： 10.1039/D1MA00007A

Hetero[8]circulenes: synthetic progress and intrinsic properties 招待有り査読有り

Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 56 巻 ( 100 ) 2020年12月

Aggregation-Induced Emission in Tetrathia[8]circulene Octaoxides via Restriction of the Dynamic Motion of their Negatively Curved pi-Frameworks 査読有り

Murase Hiroyasu, Nagata Yuya, Akahori Shuhei, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-AN ASIAN JOURNAL 15 巻 ( 22 ) 頁： 3873 - 3877 2020年11月

Site-selective halogenation on meso-mesityl substituents of 10,20-dimesityl-5,15-diazaporphyrins with an AuX3/AgOTf combination 査読有り

Longevial Jean-Francois, Miyagawa Kazuya, Shinokubo Hiroshi

DALTON TRANSACTIONS 49 巻 ( 42 ) 頁： 14786 - 14789 2020年11月

Synthesis and electron-transport properties of a stable antiaromatic Ni-II norcorrole with the smallest meso-substituent 査読有り

Ukai Shusaku, Koo Yun Hee, Fukui Norihito, Seki Shu, Shinokubo Hiroshi

DALTON TRANSACTIONS 49 巻 ( 41 ) 頁： 14383 - 14387 2020年11月

Iron(III) 5,15-Diazaporphyrin Catalysts for the Direct Oxidation of C(sp(3))-H Bonds 査読有り

Nishimura Tsubasa, Ikeue Takahisa, Shoji Osami, Shinokubo Hiroshi, Miyake Yoshihiro

INORGANIC CHEMISTRY 59 巻 ( 21 ) 頁： 15751 - 15756 2020年11月

as-Indaceno[3,2,1,8,7,6-ghijklm]terrylene as a near-infrared absorbing C-70-fragment 査読有り

Tanaka Yuki, Fukui Norihito, Shinokubo Hiroshi

NATURE COMMUNICATIONS 11 巻 ( 1 ) 2020年8月

Dinaphthothiepine Bisimide and Its Sulfoxide: Soluble Precursors for Perylene Bisimide 査読有り

Hayakawa Sakiho, Matsuo Kyohei, Yamada Hiroko, Fukui Norihito, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 142 巻 ( 27 ) 頁： 11663 - 11668 2020年7月

meso-Diazacorrphycenes: Neighboring Effect of Two Nitrogen Atoms 査読有り

Yagi Atsumi, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 26 巻 ( 37 ) 頁： 8210 - 8213 2020年7月

A 2-to-2 ' 18-to-18 ' doubly linked Ni(ii) norcorrole dimer: an effectively conjugated antiaromatic dyad 査読有り

Liu Si-Yu, Kawashima Hiroyuki, Fukui Norihito, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 56 巻 ( 50 ) 頁： 6846 - 6849 2020年6月

新形式の芳香族化合物の合成を目指して査読有り国際誌

忍久保洋

化学と教育 68 巻 ( 6 ) 頁： 268 - 269 2020年6月

担当区分：責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

反芳香族化合物は不安定な化合物であるが，それを上下に接近させて重ねると芳香族化合物になり，安定化することが分かってきた。これまで，芳香族性の起源は二次元的なπ電子の広がりであると考えられてきた。しかし最新の研究により，2つの分子の間の三次元的なπ電子の広がりによっても芳香族性が生じることが示された。また，反芳香族化合物が芳香族化合物よりも互いに接近しやすいことも分かってきた。分子が近づいて電荷が移動しやすくなるため，有機半導体などへの応用が期待される。

DOI： 10.20665/kakyoshi.68.6_268

Reactions of Antiaromatic Norcorrole Ni(II) Complex with Carbenes 査読有り

Liu Si-Yu, Fukuoka Takaki, Fukui Norihito, Shin Ji-Young, Shinokubo Hiroshi

ORGANIC LETTERS 22 巻 ( 11 ) 頁： 4400 - 4403 2020年6月

Synthesis and Crystal Packing Structures of 2,7-Diazapyrenes with Various Alkyl Groups at 1,3,6,8-Positions 査読有り

Nakazato Takumi, Matsuda Wakana, Sakurai Tsuneaki, Seki Shu, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY LETTERS 49 巻 ( 5 ) 頁： 465 - 468 2020年5月

Synthesis and properties of 5-aza-15-thiaporphyrins 招待有り査読有り

Yamashita Daisuke, Omori Hiroto, Fukui Norihito, Shinokubo Hiroshi

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 24 巻 ( 1-3 ) 頁： 84 - 89 2020年3月

Site-Selective N-Methylation of 5,15-Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues 査読有り国際共著

Chia Wen Xi, Nishijo Mayu, Kang Seongsoo, Oh Juwon, Nishimura Tsubasa, Omori Hiroto, Longevial Jean-Francois, Miyake Yoshihiro, Kim Dongho, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 26 巻 ( 12 ) 頁： 2754 - 2760 2020年2月

Site‐Selective N‐Methylation of 5,15‐Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues 査読有り国際誌

Chia Wen Xi, Nishijo Mayu, Kang Seongsoo, Oh Juwon, Nishimura Tsubasa, Omori Hiroto, Longevial Jean‐François, Miyake Yoshihiro, Kim Dongho, Shinokubo Hiroshi

Chemistry–A European Journal 26 巻 ( 12 ) 頁： 2754 - 2760 2020年2月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

N‐Alkylation significantly changes the electronic and optical properties, as well as the reactivity of nitrogen‐containing π‐conjugated molecules. In this study, it is found that treating 5,15‐diazaporphyrins with methyl triflate selectively affords the corresponding N ‐methyl‐5,15‐diazaporphyrinium cations in good yield. N‐Methylation substantially alters the electronic properties and reactivity of diazaporphyrins. The electron‐accepting properties of the N ‐methyl‐5,15‐diazaporphyrinium cations are enhanced due to their lowered LUMO level. Stabilization of the LUMO energy enables regio‐ and stereoselective Diels–Alder reactions of the cationic diazaporphyrin with cyclopentadiene. N‐Methylation also enhances the acidity of the inner NH protons, and thus, allows facile deprotonation to provide nitrogen‐substituted isoporphyrin analogues with only one NH group in the central cavity.

Theoretical Study on Open-Shell Singlet Character and Second Hyperpolarizabilities in Cofacial pi-Stacked Dimers Composed of Weak Open-Shell Antiaromatic Porphyrins 査読有り

Systematic Synthesis of Tetrathia[8]circulenes: The Influence of Peripheral Substituents on the Structures and Properties in Solution and Solid States 査読有り

Kato Shohei, Akahori Shuhei, Serizawa Yuma, Lin Xu, Yamauchi Mitsuaki, Yagai Shiki, Sakurai Tsuneaki, Matsuda Wakana, Seki Shu, Shinokubo Hiroshi, Miyake Yoshihiro

JOURNAL OF ORGANIC CHEMISTRY 85 巻 ( 1 ) 頁： 62 - 69 2020年1月

Inserting Nitrogen: An Effective Concept To Create Nonplanar and Stimuli-Responsive Perylene Bisimide Analogues 査読有り国際共著

Hayakawa Sakiho, Kawasaki Ayumi, Hong Yongseok, Uraguchi Daisuke, Ooi Takashi, Kim Dongho, Akutagawa Tomoyuki, Fukui Norihito, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141 巻 ( 50 ) 頁： 19807 - 19816 2019年12月

Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide Dimers 査読有り

Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS 21 巻 ( 23 ) 頁： 9516 - 9520 2019年12月

5,5,15,15-Tetraoxo-5,15-Dithiaporphyrin as a Highly Electron-Deficient Porphyrinic Ligand 査読有り

Yagi A.

Chemistry - A European Journal 25 巻 ( 68 ) 頁： 15580 - 15585 2019年12月

Regioselective Desilylation of a pi-Extended Aza[5]helicene

Ushiyama Ayako, Shinokubo Hiroshi, Hiroto Satoru

CHEMISTRY LETTERS 48 巻 ( 9 ) 頁： 1069 - 1072 2019年9月

Ni(II) 10-Boracorrole: An Antiaromatic Porphyrinoid Containing a Boron Atom at the meso-Position

Omori Hiroto, Shinokubo Hiroshi

ORGANOMETALLICS 38 巻 ( 15 ) 頁： 2878 - 2882 2019年8月

Soluble and Planar 2,9-Diazaperopyrenes through Reductive Aromatization of Perylene Diimides: Tunable Emission and Aggregation Behaviors

Nakamura Yasutaka, Nakazato Takumi, Kamatsuka Takuto, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL 25 巻 ( 45 ) 頁： 10571 - 10574 2019年8月

Three-dimensional aromaticity in an antiaromatic cyclophane 査読有り国際共著

Nozawa Ryo, Kim Jinseok, Oh Juwon, Lamping Anna, Wang Yemei, Shimizu Soji, Hisaki Ichiro, Kowalczyk Tim, Fliegl Heike, Kim Dongho, Shinokubo Hiroshi

NATURE COMMUNICATIONS 10 巻 2019年8月

Exploration of Li-Organic Batteries Using Hexaphyrin as an Active Cathode Material

Shin Ji-Young, Zhang Zhongyue, Awaga Kunio, Shinokubo Hiroshi

MOLECULES 24 巻 ( 13 ) 2019年7月

Synthesis of meso-Alkyl-Substituted Norcorrole-Ni-II Complexes and Conversion to 5-Oxaporphyrins(2.0.1.0)

Liu Si-Yu, Tanaka Hiroko, Nozawa Ryo, Fukui Norihito, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 25 巻 ( 32 ) 頁： 7618 - 7622 2019年6月

Synthesis of Hydroxyisooxophlorins by Oxidative Degradation of meso-Hydroxyporphyrins

Takiguchi Asahi, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS 21 巻 ( 11 ) 頁： 3950 - 3953 2019年6月

Regioselective Oxidative Ring Cleavage of Antiaromatic Nickel(II) Norcorrole to Dialkoxybis(dipyrrin)s

Shafie Siham A., Kawashima Hiroyuki, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMPLUSCHEM 84 巻 ( 6 ) 頁： 623 - 626 2019年6月

Synthesis of Dihydropyrazine-fused Porphyrin Dimers

Takiguchi Asahi, Wakita Mana, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS 48 巻 ( 4 ) 頁： 371 - 373 2019年4月

Ni(II) 10-Phosphacorrole: A Porphyrin Analogue Containing Phosphorus at the Meso Position

Omori Hiroto, Hiroto Satoru, Takeda Youhei, Fliegl Heike, Minakata Satoshi, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141 巻 ( 12 ) 頁： 4800 - 4805 2019年3月

Diazachlorin and diazabacteriochlorin for one- and two-photon photodynamic therapy 査読有り

Longevial Jean-Francois, Yamaji Ayaka, Aggad Dina, Kim Gakhyun, Chia Wen Xi, Nishimura Tsubasa, Miyake Yoshihiro, Clement Sebastien, Oh Juwon, Daurat Morgane, Nguyen Christophe, Kim Dongho, Gary-Bobo Magali, Richeter Sebastien, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 54 巻 ( 98 ) 頁： 13829 - 13832 2018年12月

Fujiyoshi Jun-Ya, Tonami Takayoshi, Yamane Masaki, Okada Kenji, Kishi Ryohei, Muhammad Shabbir, Al-Sehemi Abdullah G., Nozawa Ryo, Shinokubo Hiroshi, Nakano Masayoshi

CHEMPHYSCHEM 19 巻 ( 21 ) 頁： 2863 - 2871 2018年11月

X-Shaped Cyclobutane-Linked Tetraporphyrins through a Thermal [2+2] Cycloaddition of Etheno-Fused Diporphyrins 査読有り

Nagai Tomohiro, Takiguchi Asahi, Ueda Masayuki, Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140 巻 ( 27 ) 頁： 8392-8395 2018年7月

Azabuckybowl-Based Molecular Tweezers as C-60 and C-70 Receptors 査読有り

Takeda Motoki, Hiroto Satoru, Yokoi Hiroki, Lee Sangsu, Kim Dongho, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140 巻 ( 20 ) 頁： 6336-6342 2018年5月

The reductive aromatization of naphthalene diimide: a versatile platform for 2,7-diazapyrenes 査読有り

Nakazato Takumi, Kamatsuka Takuto, Inoue Junichi, Sakurai Tsuneaki, Seki Shu, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS 54 巻 ( 41 ) 頁： 5177-5180 2018年5月

Reversible sigma-Bond Formation in Bowl-Shaped pi-Radical Cations: The Effects of Curved and Planar Structures 査読有り

Yokoi Hiroki, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140 巻 ( 13 ) 頁： 4649-4655 2018年4月

Figuration of bowl-shaped pi-conjugated molecules: properties and functions 招待有り査読有り

Saito Masaichi, Shinokubo Hiroshi, Sakurai Hidehiro

MATERIALS CHEMISTRY FRONTIERS 2 巻 ( 4 ) 頁： 635 - 661 2018年4月

Benzonorcorrole Ni-II Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo-Fusion 査読有り

Yoshida Takuya, Takahashi Kohtaro, Ide Yuki, Kishi Ryohei, Fujiyoshi Jun-ya, Lee Sangsu, Hiraoka Yuya, Kim Dongho, Nakano Masayoshi, Ikeue Takahisa, Yamada Hiroko, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57 巻 ( 8 ) 頁： 2209-2213 2018年2月

Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C-60 査読有り

Yokoi Hiroki, Hiroto Satoru, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

CHEMICAL SCIENCE 9 巻 ( 4 ) 頁： 819-824 2018年1月

Synthesis and Photodynamics of Tetragermatetrathia[8]circulene 査読有り

Akahori Shuhei, Sakai Hayato, Hasobe Taku, Shinokubo Hiroshi, Miyake Yoshihiro

ORGANIC LETTERS 20 巻 ( 1 ) 頁： 304-307 2018年1月

Nickel (II) pyrrocorphin: Enhanced binding ability in a highly reduced porphyrin complex 査読有り

Ide Yuki, Kuwahara Takamitsu, Takeshita Syo, Fujishiro Rei, Suzuki Masaaki, Mori Shigeki, Shinokubo Hiroshi, Nakamura Mikio, Yoshino Katsumi, Ikeue Takahisa

JOURNAL OF INORGANIC BIOCHEMISTRY 178 巻頁： 115 - 124 2018年1月

Synthesis of Heteroatom-Containing Curved pi-Conjugated Molecules 査読有り

Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 76 巻 ( 1 ) 頁： 37-44 2018年1月

ヘテロ元素を含む曲面π共役分子合成法の開発査読有り国際誌

廣戸聡, 忍久保洋

有機合成化学協会誌 76 巻 ( 1 ) 頁： 37 - 44 2018年

Structures of the Heme Acquisition Protein HasA with Iron(III)-5,15-Diphenylporphyrin and Derivatives Thereof as an Artificial Prosthetic Group 査読有り

Uehara Hiromu, Shisaka Yuma, Nishimura Tsubasa, Sugimoto Hiroshi, Shiro Yoshitsugu, Miyake Yoshihiro, Shinokubo Hiroshi, Watanabe Yoshihito, Shoji Osami

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 56 巻 ( 48 ) 頁： 15279 - 15283 2017年11月

Acid-Mediated Migration of Bromide in an Antiaromatic Porphyrinoid: Preparation of Two Regioisomeric Ni(II) Bromonorcorroles 査読有り

Kawashima Hiroyuki, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF ORGANIC CHEMISTRY 82 巻 ( 19 ) 頁： 10425 - 10432 2017年10月

Shaping Antiaromatic -Systems by Metalation: Synthesis of a Bowl-Shaped Antiaromatic Palladium Norcorrole 査読有り

Yonezawa Tsubasa, Shafie Siham A., Hiroto Satoru, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 56 巻 ( 39 ) 頁： 11822 - 11825 2017年9月

Synthesis and Properties of meso-Arylated Corrphycenes 査読有り

Nozawa Ryo, Shinokubo Hiroshi

ORGANIC LETTERS 19 巻 ( 18 ) 頁： 4928 - 4931 2017年9月

Design and Synthesis of Tunable Ligands with 4,4'-Bipyridyl as an Electron-Accepting Unit and Their Rhenium Complexes 査読有り

Kamatsuka Takuto, Shinokubo Hiroshi, Miyake Yoshihiro

ORGANOMETALLICS 36 巻 ( 17 ) 頁： 3429 - 3434 2017年9月

A synthesis of novel expanded porphyrinoids: Ni-II-induced nitrile cyclization of dicyanovinylene-bis (meso-aryl)dipyrrin 査読有り

Faialaga Nathan H., Ito Satoru, Shinokubo Hiroshi, Kim Younghoon, Kim Kimoon, Shin Ji-Young

DALTON TRANSACTIONS 46 巻 ( 33 ) 頁： 10802 - 10808 2017年9月

pi-Extended Dihydrophenazines with Three-State NIR Electrochromism Involving Large Conformational Changes 査読有り

Nagasaki Juri, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-AN ASIAN JOURNAL 12 巻 ( 17 ) 頁： 2311 - 2317 2017年9月

Direct amination of the antiaromatic Ni-II norcorrole 査読有り

Yoshida Takuya, Shinokubo Hiroshi

MATERIALS CHEMISTRY FRONTIERS 1 巻 ( 9 ) 頁： 1853 - 1857 2017年9月

Selective alpha-arylation of alpha,beta-unsaturated imides mediated by a visible light photoredox catalyst

Ando Yuki, Kamatsuka Takuto, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS 53 巻 ( 65 ) 頁： 9136-9138 2017年8月

Highly-conducting molecular circuits based on antiaromaticity 査読有り

Fujii Shintaro, Marques-Gonzalez Santiago, Shin Ji-Young, Shinokubo Hiroshi, Masuda Takuya, Nishino Tomoaki, Arasu Narendra P., Vazquez Hector, Kiguchi Manabu

NATURE COMMUNICATIONS 8 巻 2017年7月

Synthesis, Properties, and Reactivities of Ruthenium(II) Carbonyl 5,15-Diazaporphyrins 査読有り

Nishimura Tsubasa, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMISTRY LETTERS 46 巻 ( 7 ) 頁： 995 - 997 2017年7月

NIR mechanochromic behaviours of a tetracyanoethylene-bridged hexa-peri-hexabenzocoronene dimer and trimer through dissociation of C-C bonds 査読有り

Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF MATERIALS CHEMISTRY C 5 巻 ( 22 ) 頁： 5310 - 5315 2017年6月

NIR mechanochromic behaviours of a tetracyanoethylene-bridged hexa-peri-hexabenzocoronene dimer and trimer through dissociation of C–C bonds 査読有り国際誌

Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

Journal of Materials Chemistry C 5 巻 ( 22 ) 頁： 5310 - 5315 2017年6月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Oxidation of dicyanomethyl-substituted hexa-peri-hexabenzocoronenes (HBCs) furnished a tetracyanoethylene-bridged HBC dimer and trimer. The solid state structures of the oligomers were elucidated using single crystal X-ray diffraction analysis. In the solution state, these HBC oligomers exhibited conformational isomerism, depending on solvents and temperatures. Moreover, solid samples of the HBC dimer and trimer exhibited mechanochromism, showing near IR absorption upon grinding through generation of radical species. The formed radical was stable for 4 months, indicating the persistent nature of the radical species. These NIR mechanochromic behaviours of the HBC oligomers were originated from the reversible C–C bond dissociation and formation of a tetracyanoethylene linkage between the HBC units.

10-Silacorroles Exhibiting Near-Infrared Absorption and Emission

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 23 巻 ( 33 ) 頁： 7866-7870 2017年6月

10-Silacorroles Exhibiting NIR Absorption and Emission 査読有り国際誌

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 22 巻 ( 33 ) 頁： 7866 - 7870 2017年6月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

10-Silacorroles were obtained from the Pd-catalyzed silylative cyclization of a bis(α,α′-dibromodipyrrin) Ni^II precursor with dihydrosilanes. These 10-silacorroles show substantially red-shifted absorption bands relative to those of normal porphyrins and isocorroles. Notably, the corresponding free base and Zn^II 10-silacorroles exhibit emissions in the NIR region. Theoretical calculations on these 10-silacorroles revealed the presence of σ*–π* conjugation between the silyl group and the tetrapyrrole π system, which significantly lowers their LUMO energy levels.

Synthesis of Tetrasilatetrathia[8]circulenes by a Fourfold Intramolecular Dehydrogenative Silylation of C-H Bonds 査読有り

Serizawa Yuma, Akahori Shuhei, Kato Shohei, Sakai Hayato, Hasobe Taku, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 23 巻 ( 29 ) 頁： 6948 - 6952 2017年5月

Synthesis of Tetraaza[8]circulenes from Tetrathia[8]circulenes through an SNAr-Based Process 査読有り

Nagata Yuya, Kato Shohei, Miyake Yoshihiro, Shinokubo Hiroshi

ORGANIC LETTERS 19 巻 ( 10 ) 頁： 2718 - 2721 2017年5月

Synthesis of a figure-eight azahelicene dimer with high emission and CPL properties

Ushiyama Ayako, Hiroto Satoru, Yuasa Junpei, Kawai Tsuyoshi, Shinokubo Hiroshi

ORGANIC CHEMISTRY FRONTIERS 4 巻 ( 5 ) 頁： 664-667 2017年5月

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies 招待有り査読有り

Hiroto Satoru, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL REVIEWS 117 巻 ( 4 ) 頁： 2910 - 3043 2017年2月

Synthesis of bright red-emissive dicyanoetheno-bridged hexa-peri-hexabenzocoronene dimers 査読有り

Oda Kazuma, Hiroto Satoru, Hisaki Ichiro, Shinokubo Hiroshi

ORGANIC & BIOMOLECULAR CHEMISTRY 15 巻 ( 6 ) 頁： 1426 - 1434 2017年2月

Enhancing the low-energy absorption band and charge mobility of antiaromatic Ni-II norcorroles by their substituent effects 査読有り

Yoshida Takuya, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 53 巻 ( 6 ) 頁： 1112 - 1115 2017年1月

Stacked antiaromatic porphyrins 査読有り国際誌

Nozawa Ryo, Tanaka Hiroko, Cha Won-Young, Hong Yongseok, Hisaki Ichiro, Shimizu Soji, Shin Ji-Young, Kowalczyk Tim, Irle Stephan, Kim Dongho, Shinokubo Hiroshi

NATURE COMMUNICATIONS 7 巻頁： 13620 2016年11月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Nature Communications

Aromaticity is a key concept in organic chemistry. Even though this concept has already been theoretically extrapolated to three dimensions, it usually still remains restricted to planar molecules in organic chemistry textbooks. Stacking of antiaromatic π-systems has been proposed to induce three-dimensional aromaticity as a result of strong frontier orbital interactions. However, experimental evidence to support this prediction still remains elusive so far. Here we report that close stacking of antiaromatic porphyrins diminishes their inherent antiaromaticity in the solid state as well as in solution. The antiaromatic stacking furthermore allows a delocalization of the π-electrons, which enhances the two-photon absorption cross-section values of the antiaromatic porphyrins. This feature enables the dynamic switching of the non-linear optical properties by controlling the arrangement of antiaromatic π-systems on the basis of intermolecular orbital interactions.

DOI： 10.1038/ncomms13620

Reversible Carbon-Carbon Bond Breaking and Spin Equilibria in Bis(pyrimidinenorcorrole) 査読有り国際誌

Liu Bin, Yoshida Takuya, Li Xiaofang, Stepien Marcin, Shinokubo Hiroshi, Chmielewski Piotr J.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 55 巻 ( 42 ) 頁： 13142 - 13146 2016年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Reversible homolytic dissociation of the bis(pyrimidinenorcorrole) σ-dimer was elucidated by means of variable temperature ESR and1H NMR spectroscopy, mass spectrometry, and optical spectrocopy. Dehydrogenation of the σ-dimer yielded another dimer displaying a singlet–triplet equilibrium in solution, strong NIR absorption (1570 nm), and a narrow electrochemical HOMO–LUMO gap (0.74 V).

DOI： 10.1002/anie.201607237

Syntheses and Properties of Antiaromatic Porphyrinoids 査読有り国際誌

Satoru Hiroto, Hiroshi Shinokubo

Handbook of Porphyrin Science (Volumes 36 – 40) 2016年7月

beta-to-beta 2,5-Pyrrolylene-Linked Cyclic Porphyrin Oligomers 査読有り国際誌

Rao Yutao, Kim Jun Oh, Kim Woojae, Zhong Guangming, Yin Bangshao, Zhou Mingbo, Shinokubo Hiroshi, Aratani Naoki, Tanaka Takayuki, Liu Shubin, Osuka Atsuhiro, Kim Dongho, Song Jianxin

CHEMISTRY-A EUROPEAN JOURNAL 22 巻 ( 26 ) 頁： 8801 - 8804 2016年6月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

β-to-β 2,5-Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki–Miyaura coupling of 2,5-diborylpyrrole and 3,7-dibromoporphyrin. The cyclic porphyrin oligomers exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO–LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge.

DOI： 10.1002/chem.201601306

Synthesis of Free-Base 10-Azacorroles 査読有り国際誌

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

ORGANIC LETTERS 18 巻 ( 12 ) 頁： 2978 - 2981 2016年6月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Publications

A novel synthetic protocol has been developed for free-base 10-azacorroles. Ni(0)-mediated homocoupling of nitrogen-bridged bisdipyrrin Zn(II) complexes afforded a series of free-base 5,15-diaryl-10-azacorroles in good yields. Pd(II) and Cu(II) complexes have been prepared through metalation of free-base 10-azacorroles. Optical and electrochemical properties of 10-azacorrole metal complexes can be tuned by meso-aryl substituents and central metals. Cyclic voltammetry and theoretical calculations elucidated that the central metals of 10-azacorroles significantly affected their electronic properties.

DOI： 10.1021/acs.orglett.6b01323

Fully-substituted 1,3-Butadienes as pi-Conjugated Linkers between Pyrenes 査読有り国際誌

Oda Kazuma, Hiroto Satoru, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

CHEMISTRY LETTERS 45 巻 ( 4 ) 頁： 403 - 405 2016年4月

担当区分：最終著者,　責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

Pyrenyl-substituted 1,3-butadienes bearing alkyl and aryl groups have been synthesized by palladium-catalyzed addition of 2-borylpyrene to internal alkynes. On UV irradiation, 1-pyrenylbutadienes undergo photochromism in solution. In the solid state, 1-pyrenyl-1,2,3,4-tetraaryl-1,3-butadiene exhibits red-shifted and broad emission as compared with the alkylated butadiene. The charge-carrier mobility of 1-pyrenyl-1,2,3,4-tetraalkyl-1,3-butadiene is higher than that of the arylated butadiene.

DOI： 10.1246/cl.151181

Control of Conformation and Chirality of Nonplanar pi-Conjugated Diporphyrins Using Substituents and Axial Ligands 査読有り国際誌

Ito Satoru, Hiroto Satoru, Ousaka Naoki, Yashima Eiji, Shinokubo Hiroshi

CHEMISTRY-AN ASIAN JOURNAL 11 巻 ( 6 ) 頁： 936 - 942 2016年3月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - An Asian Journal

Nonplanar conformations of pyrazine-fused ZnII diporphyrins could be controlled by the choice of the meso-aryl substituents and an axial ligand on the central metals. ZnII diporphyrins bearing sterically demanding meso-aryl groups with ortho-substituents led to a twisted chiral D2 conformation, while an achiral C2h form was preferred in the case of aryl groups without ortho-substituents. Helical chirality induction on ZnII diporphyrins in the twisted conformation was achieved by controlling their handedness of the molecular twist through coordination of optically active 1-phenethylamine. But there′s a twist! Conformations of nonplanar ZnII diporphyrins could be controlled by the meso-aryl substituents and an axial ligand on the central metals. Helical chirality induction on ZnII diporphyrins was achieved by controlling their handedness of the molecular twist through coordination of an optically active amine.

DOI： 10.1002/asia.201600105

Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids 査読有り国際誌

Yamaji Ayaka, Tsurugi Hayato, Miyake Yoshihiro, Mashima Kazushi, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 22 巻 ( 12 ) 頁： 3956 - 3961 2016年3月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

Reagent-controlled chemo- and regioselective reduction of 5,15-diazaporphyrins has been developed. The selective reduction of carbon-carbon double bonds of diazaporphyrins provides 18 π aromatic isobacteriochlorin-type products, whereas the reduction of carbon-nitrogen double bonds leads to selective formation of 20 π N,N′-dihydrodiazaporphyrins in excellent yields. The distinct antiaromatic character of N,N′-dihydrodiazaporphyrins has been revealed. The free-base N,N′-dihydrodiazaporphyrin exhibits slower inner NH tautomerism than that in the corresponding 18 π porphyrins. Reagent-controlled chemo- and regioselective reduction of 5,15-diazaporphyrins has been developed. The selective reduction of carbon-carbon double bonds of diazaporphyrins provides aromatic isobacteriochlorin-type products, whereas the reduction of carbon-nitrogen double bonds leads to N,N′-dihydrodiazaporphyrins with distinct antiaromatic character.

DOI： 10.1002/chem.201600066

脱炭酸的アリール化によるグラフェン量子ドットの可溶化と発光色の制御査読有り国際誌

小田一磨, 廣戸聡, 忍久保洋

応用物理学会学術講演会講演予稿集 2016.1 巻 ( 0 ) 頁： 3881 - 3881 2016年3月

The synthesis of Ni-II and Al-III 10-azacorroles through coordination-induced cyclisation involving 1,2-migration 査読有り国際誌

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 52 巻 ( 17 ) 頁： 3540 - 3543 2016年

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

We have synthesized NiII and AlIII 10-azacorroles through coordination-induced cyclisation of nitrogen-bridged bisdipyrrins. AlIII 10-azacorrole displayed contrasting optoelectronic behaviours from NiII 10-azacorrole, underlining the different electronic effects of the azacorrole ligand from the porphyrin.

DOI： 10.1039/c5cc10247b

Ni-II tetrahydronorcorroles: antiaromatic porphyrinoids with saturated pyrrole units 査読有り国際誌

Nozawa Ryo, Yamamoto Keitaro, Hisaki Ichiro, Shin Ji-Young, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 52 巻 ( 44 ) 頁： 7106 - 7109 2016年

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

While hydrogenated porphyrins are abundant in natural and synthetic compounds, antiaromatic hydrogenated porphyrinoids have not been synthesized to date. Here, we report bacteriochlorin-like NiII tetrahydronorcorrole complexes as the first examples of antiaromatic porphyrinoids that contain saturated pyrrole units.

DOI： 10.1039/c6cc02918c

Indolylindolinone: Easily Accessible, Tunable, and Wide-range Absorbing Dyes 査読有り国際誌

Shigeno Ami, Matsuno Takashi, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS 44 巻 ( 12 ) 頁： 1703 - 1705 2015年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

Dehydrative coupling between indoles and isatins provided indolylindolinones in good yields as novel dyes with wide-range absorption due to intramolecular charge-transfer interactions. The HOMO and LUMO levels of indolylindolinones could be manipulated individually by the introduction of substituents on the indole and isatin units, respectively. Indolylindolinones served as a bidentate ligand to Ni(II) and Cu(II) ions to provide stable metal complexes. Metal coordination induced large bathochromic shift of the lowest-energy absorption band to the near-infrared region.

DOI： 10.1246/cl.150815

Twisting of π-conjugated plane to one rotation 査読有り国際誌

Hiroto S., Shinokubo H.

Kobunshi 64 巻 ( 11 ) 頁： 713 - 714 2015年11月

担当区分：責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Kobunshi

We have established the facile and efficient protocol to synthesize distorted 71-conjugated molecules. Oxidation of amino-substituted porphyrins proceeded with high regioselectivity to produce pyrazine fused dimers. X-ray diffraction analysis revealed its highly twisted structure. Electrochemical and optical measurements indicated the twisting mostly influences on HOMO. The sequential use of our protocol has achieved the synthesis of unidirectionally twisted porphyrin tetramers efficiently. NMR analysis suggested that the racemization barrier of twisting increases on oligomerization. To the best of our knowledge, this is the first observation of a similar phenomenon observed in polymer science for twisted, jt-conjugated molecules. The present findings represent an important advance towards the long-term goal of preparing -conjugated molecular wires, whose properties can be fine-tuned through molecular twisting.

A Stable Organic -Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin 査読有り国際誌

Tanaka Yasuo, Yoneda Tomoki, Furukawa Ko, Koide Taro, Mori Hirotaka, Tanaka Takayuki, Shinokubo Hiroshi, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54 巻 ( 37 ) 頁： 10908 - 10911 2015年9月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

A ZnII-CuI-ZnII heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a [46]decaphyrin with ZnII ions to produce a 46π decaphyrin bis(ZnII) complex and its subsequent metalation with CuII ion. In the second metalation step, it has been shown that CuII ion is reduced to a CuI ion in the complex and a dianionic bis(ZnII) containing [46]decaphyrin ligand is oxidized to the corresponding monoanionic [45]decaphyrin ligand, indicating a non-innocent nature of the decaphyrin ligand. Despite the radical nature, the heterotrimetal complex is fairly stable under ambient conditions and exhibits almost no intermolecular magnetic interaction, owing to extensive delocalization of an unpaired electron in the large π-conjugated circuit of decaphyrin moiety. Radical racetrack: CuII metalation of a [46]decaphyrin bis(ZnII) complex gave a ZnII-CuI-ZnII heterotrimetal complex of decaphyrin consisting of a central CuI ion and a monoanionic 45π radical of decaphyrin.

DOI： 10.1002/anie.201505130

Nitrogen-embedded buckybowl and its assembly with C[60] 査読有り国際誌

Yokoi Hiroki, Hiraoka Yuya, Hiroto Satoru, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

Nature Communications 6 巻 2015年9月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Curved π-conjugated molecules have attracted considerable interest because of the unique properties originating from their curved π surface. However, the synthesis of such distorted molecules requires harsh conditions, which hamper easy access to heteroatom-containing curved π systems. Here we report the synthesis of a π-extended azacorannulene with nitrogen in its centre. The oxidation of 9-aminophenanthrene provides tetrabenzocarbazole, which is converted to the azabuckybowl through palladium-catalysed intramolecular coupling. The electron-donating nature and curved π surface of the azabuckybowl enable its tight association with C[60] in solution and solid states. High charge mobility is observed for the azabuckybowl/C[60] assembly. This compound may be of interest in the fields of curved π systems as fullerene hosts, anisotropic π donors and precursors to nitrogen-containing nanocarbon materials.

Nitrogen-embedded buckybowl and its assembly with C-60 査読有り国際誌

Yokoi Hiroki, Hiraoka Yuya, Hiroto Satoru, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

NATURE COMMUNICATIONS 6 巻頁： 8215 2015年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Nature Communications

Curved π-conjugated molecules have attracted considerable interest because of the unique properties originating from their curved π surface. However, the synthesis of such distorted molecules requires harsh conditions, which hamper easy access to heteroatom-containing curved π systems. Here we report the synthesis of a π-extended azacorannulene with nitrogen in its centre. The oxidation of 9-aminophenanthrene provides tetrabenzocarbazole, which is converted to the azabuckybowl through palladium-catalysed intramolecular coupling. The electron-donating nature and curved π surface of the azabuckybowl enable its tight association with C60 in solution and solid states. High charge mobility is observed for the azabuckybowl/C60 assembly. This compound may be of interest in the fields of curved π systems as fullerene hosts, anisotropic π donors and precursors to nitrogen-containing nanocarbon materials.

DOI： 10.1038/ncomms9215

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles 査読有り国際誌

Nozawa Ryo, Yamamoto Keitaro, Shin Ji-Young, Hiroto Satoru, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54 巻 ( 29 ) 頁： 8454 - 8457 2015年7月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3-cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO-LUMO gap and enhanced the near IR absorption property.

DOI： 10.1002/anie.201502666

Synthesis of Highly Twisted and Fully pi-Conjugated Porphyrinic Oligomers 査読有り国際誌

Ito Satoru, Hiroto Satoru, Lee Sangsu, Son Minjung, Hisaki Ichiro, Yoshida Takuya, Kim Dongho, Kobayashi Nagao, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137 巻 ( 1 ) 頁： 142 - 145 2015年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Highly twisted π-conjugated molecules have been attractive but challenging targets. We report here an efficient synthesis of highly twisted diporphyrins with 126° and 136° twist angles that involves an oxidative fusion reaction of planar aminoporphyrin precursors at room temperature. Repeated amination-oxidative fusion sequences provide a unidirectionally twisted tetramer. The twisting angle of the tetramer is 298°.

DOI： 10.1021/ja511905f

PALLADIUM-CATALYZED [3+2] ANNULATION OF meso-BROMOPORPHYRINS WITH SILYLACETYLENES AND DESILYLATION OF 8(a)-SILYL-7,8-DEHYDROPURPURIN 査読有り国際誌

Fukui Norihito, Arai Seiji, Shinokubo Hiroshi, Yorimitsu Hideki, Osuka Atsuhiro

HETEROCYCLES 90 巻 ( 1 ) 頁： 252 - 260 2015年1月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Heterocycles

Palladium-catalyzed [3+2] annulation of meso-bromoporphyrins with trimethylsilyl-, tert-butyldimethylsilyl-, and triisopropylsilylacetylenes afforded 8a-silyl-7,8-dehydropurpurins. Protodesilylation of 8a-trimethylsilyl-7,8-dehydropurpurin resulted in the first synthesis of an 8a,8b-unsubstituted 7,8-dehydropurpurin.

DOI： 10.3987/COM-14-S(K)15

Synthesis of Novel Porphyrinoids from Dipyrrins 招待有り査読有り国際誌

Hiroshi Shinokubo

Chemical Science of Electron Systems 頁： 243 - 255 2015年1月

担当区分：筆頭著者,　最終著者,　責任著者記述言語：英語掲載種別：論文集(書籍)内論文出版者・発行元：Springer Japan

Most syntheses of meso-substituted porphyrinoid rely on acid-catalyzed condensation of pyrrole segments with aldehyde units followed by oxidation. This standard procedure is convenient but generally is low yielding. However, modern synthetic methodologies would offer an expeditious route to several intriguing porphyrinoids. In particular, the metal template strategy using dipyrrin metal complexes is effective to construct porphyrin-like cyclic π-conjugated systems, which are otherwise difficult to access by the conventional methodology.

DOI： 10.1007/978-4-431-55357-1_14

Selective Synthesis of a [32]Octaphyrin(1.0.1.0.1.0.1.0) Bis(palladium) Complex by a Metal‐Templated Strategy 国際誌

Diversity-oriented synthesis of tetrathia[8]circulenes by sequential C-H borylation and annulation 査読有り国際誌

Kato Shohei, Serizawa Yuma, Sakamaki Daisuke, Seki Shu, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 51 巻 ( 95 ) 頁： 16944 - 16947 2015年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

We have succeeded in the diversity-oriented synthesis of tetrathia[8]circulenes by sequential C-H borylation and annulation from cyclic tetrathiophene, and time-resolved microwave conductivity studies have proved that the intrinsic hole mobilities of tetrathia[8]circulenes are dependent on the chain length of the alkyl substituents at the peripheral positions.

DOI： 10.1039/c5cc06921a

Macrocyclic dipyrrin dimer bridged by ethylene and dioxyphenylene linkers 査読有り国際誌

Shin Ji-Young, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 19 巻 ( 1-3 ) 頁： 135 - 139 2015年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Porphyrins and Phthalocyanines

A tetrapyrrolic macrocycle containing ethenylene and dioxyphenylene bridges was obtained through the reaction of a dipyrrin-DDQ adduct with triethylamine. The structure of the macrocycle was elucidated by X-ray diffraction analysis. The macrocycle exhibited solvent-dependent absorption spectra due to intramolecular charge transfer interactions.

DOI： 10.1142/S108842461450093X

Isolation of a 1,4-diketone intermediate in oxidative dimerization of 2-hydroxyanthracene and its conversion to oxahelicene 査読有り国際誌

Matsuno Takashi, Koyama Yutaro, Hiroto Satoru, Kumar Jatish, Kawai Tsuyoshi, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 51 巻 ( 22 ) 頁： 4607 - 4610 2015年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

Oxidation of 2-hydroxy-9,10-dialkynylanthracenes resulted in highly regioselective dimerization to furnish metastable dearomatized 1,4-diketones rather than stable aromatic diols. The 1,4-diketones were converted to oxahelicenes, which exhibited strong fluorescence both in solution and solid state as well as chiroptical properties. This journal is

DOI： 10.1039/c5cc00764j

A 3-Pyridyl-5,15-Diazaporphyrin Nickel(II) Complex as a Bidentate Metalloligand for Transition Metals 査読有り国際誌

Yamaji Ayaka, Shin Ji-Young, Miyake Yoshihiro, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 巻 ( 50 ) 頁： 13924 - 13927 2014年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

3-Pyridyl-5,15-diazaporphyrin nickel(II) serves as a bidentate metalloligand for platinum(II), ruthenium(II), and rhenium(I) metal centers. Single-crystal X-ray diffraction analysis of these metal complexes unambiguously reveals the presence of a dative bond between the outer metal center and the meso-nitrogen atom. The UV/Vis absorption spectra of the complexes show substantially red-shifted bands which are perturbed by outer-metal coordination. This is due to the contribution of metal-to-ligand charge transfer interactions.

DOI： 10.1002/anie.201408852

Synthesis of Curved Hexa-peri-hexabenzocoronenes 査読有り国際誌

Yamaguchi Ryuichi, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS 43 巻 ( 10 ) 頁： 1637 - 1639 2014年10月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

Halogenation and phenylthiolation of hexabenzocoronenetetraone were performed. We found that introduction of substituents at the fjord regions induced substantial curvature of the hexabenzocoronene (HBC) plane through steric repulsion between the substituents and proximal hydrogen atoms. This method allows construction of curved HBC derivatives, which would allow formation of novel supramolecular structures.

DOI： 10.1246/cl.140577

Regioselective Double Cyclization of 5,15-Bis(trimethylsilylethynyl)porphyrin to Produce Di(oxoethano)porphyrin 査読有り国際誌

Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS 43 巻 ( 9 ) 頁： 1444 - 1446 2014年9月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

Treatment of bis(trimethylsilylethynyl)porphyrin with strong acids afforded doubly oxoethano-fused porphyrin with perfect regioselectivity. The oxoethano-fused porphyrin was more electron deficient than meso-acetylporphyrin because of the coplanar orientation of the carbonyl groups to the porphyrin π system.

DOI： 10.1246/cl.140470

Facile Synthesis of Nitrogen-containing Polycyclic Aromatic Hydrocarbons from Perylene Bisimides 査読有り国際誌

Ito Satoru, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS 43 巻 ( 8 ) 頁： 1309 - 1311 2014年8月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

We have developed a facile procedure for the synthesis of π-extended fluorubins from perylene bisimides. Iridium-catalyzed direct borylation, the Suzuki–Miyaura cross-coupling, and an acid-condensation sequence afforded π-extended fluorubins 1 in moderate yields. X-ray diffraction analysis revealed a planar structure of 1. In addition, optical analysis and DFT calculations indicated the presence of intramolecular charge-transfer interactions in 1c.

DOI： 10.1246/cl.140330

Synthesis of Diazo-Bridged BODIPY Dimer and Tetramer by Oxidative Coupling of beta-Amino-Substituted BODIPYs 査読有り国際誌

Yokoi Hiroki, Hiroto Satoru, Shinokubo Hiroshi

ORGANIC LETTERS 16 巻 ( 11 ) 頁： 3004 - 3007 2014年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

A diazo-bridged BODIPY dimer and tetramer were prepared by the oxidative coupling reaction of β-amino-substituted BODIPYs. The structure of the dimer was elucidated by X-ray diffraction analysis, showing its coplanar orientation of two BODIPY units. Effective extension of π-conjugation was confirmed by optical and electrochemical investigations. © 2014 American Chemical Society.

DOI： 10.1021/ol501131j

Photodynamics of [26]- and [28]Hexaphyrin-Bodipy Hybrids 査読有り国際誌

Shin Ji-Young, Kim Kilsuk, Lim Jong Min, Tanaka Takayuki, Kim Dongho, Kim Kimoon, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY-A EUROPEAN JOURNAL 20 巻 ( 16 ) 頁： 4574 - 4582 2014年4月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties, given by uses of phenylene, biphenylene, and triphenyelene bridges was prepared. Efficient PET processes from bodipy (donor) to [26]- or [28]hexaphyrin (acceptor) were successfully observed, where the PET speed was controlled by intramolecular distances between the donor and the acceptor. UV irradiation at 515 nm raised a band corresponding to the bodipy absorption. As the time delayed, the bodipy bands decreased and new absorption bands at 615 and 580 nm corresponding to respective absorption bands of [28]- and [26]-hybrids gradually appeared. Whereas the femtosecond transient absorption spectra of [28]/[26]-hybrids having terphenylene bridges completely showed energy transfers from bodipy to hexaphyrin, irradiation of the hybrids using 615 and 580 nm pulses did not induce opposite ways of the PET process. On the basis of enlarged center-to-center-distances of [26]-hybrids than those of [28]-hybrids, the set of [26]-hybrids resulted in slow decay/rise processes. PET parameters obtained with the experiments were fairly consistent with the PET parameters calculated. Speed control: A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties was prepared (see figure). Efficient PET processes from bodipy to [26]/[28]hexaphyrin were successfully observed on terphenylene-containing hybrids. [26]-Hybrids performed slower speeds of decay/rise processes than [28]-hybrids on the basis of enlarged center-to-center distances. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/chem.201400315

Silylethynyl Substituents as Porphyrin Protecting Groups for Solubilization and Selectivity Control 査読有り国際誌

Oda Kazuma, Akita Masanari, Hiroto Satoru, Shinokubo Hiroshi

ORGANIC LETTERS 16 巻 ( 6 ) 頁： 1818 - 1821 2014年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

Silylethynyl substituents are proposed as protecting groups for porphyrin derivatives to enhance their solubility and enable regioselective functionalization. After usage as protecting groups, silylethynyl groups at the meso-positions can be efficiently removed upon heating with aqueous H 2SO4 in the presence of a surfactant. This approach was applied to the preparation of unsymmetrically β-substituted porphyrins and porphin-porphyrin oligomers, which were inaccessible by conventional methods. © 2014 American Chemical Society.

DOI： 10.1021/ol500569b

An Antiaromatic Electrode-Active Material Enabling High Capacity and Stable Performance of Rechargeable Batteries 査読有り国際誌

Shin Ji-Young, Yamada Tetsuya, Yoshikawa Hirofumi, Awaga Kunio, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 巻 ( 12 ) 頁： 3096 - 3101 2014年3月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Although aromatic compounds occupy a central position in organic chemistry, antiaromatic compounds have demonstrated little practical utility. Herein we report the application of an antiaromatic compound as an electrode-active material in rechargeable batteries. The performance of dimesityl-substituted norcorrole nickel(II) complex (NiNC) as a cathode-active material was examined with a Li metal anode. A maximum discharge capacity of about 207 mAhg -1 was maintained after 100 charge/discharge cycles. Moreover, the bipolar redox property of NiNC enables the construction of a Li metal free rechargeable battery. The high performance of NiNC batteries demonstrates a prospective feature of stable antiaromatic compounds as electrode-active materials. The balance of power: A discharge capacity of greater than 200 mA h g-1 over 100 charge/discharge cycles was found for a rechargeable battery with an antiaromatic norcorrole NiII complex (NiNC) as a cathode-active material and a Li metal anode. The bipolar redox property of NiNC also enabled the construction of a Li metal free rechargeable battery with high discharge capacity (see scheme) and good cycle performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201310374

Synthesis of Novel Porphyrinoids through Organometallic Means 査読有り国際誌

Shinokubo Hiroshi

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 72 巻 ( 2 ) 頁： 149 - 157 2014年2月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人有機合成化学協会

Porphyrin is a representative functional molecule, which consists of four pyrrole units linked by four carbon atoms with an 18/r aromatic character. Most of porphyrin syntheses rely on acid- catalyzed condensation of pyrrole with aldehydes followed by oxidation, which are low-yielding in many cases. To establish more effective porphyrin synthesis, we have devoted our effort to combine porphyrin chemistry and modern organic synthesis through transition metal-mediated reactions. In this article, we focus on synthesis of novel porphyrin analogues through coupling of dipyrrin precursors. The metal-templated strategy using dipyrrin metal complexes was found to be quite efficient to construct porphyrin-like cyclic π-conjugated systems consisting of the dipyrrin unit, which exhibit intriguing optical and electronic properties.

DOI： 10.5059/yukigoseikyokaishi.72.149

有機金属化学的手法による新規ポルフィリン類縁体の合成査読有り国際誌

忍久保洋

有機合成化学協会誌 = Journal of synthetic organic chemistry, Japan 72 巻 ( 2 ) 頁： 149 - 157 2014年2月

Near‐IR Absorbing Nickel(II) Porphyrinoids Prepared by Regioselective Insertion of Silylenes into Antiaromatic Nickel(II) Norcorrole 国際共著国際誌

Takaki Fukuoka, Kenya Uchida, Young Mo Sung, Ji‐Young Shin, Shintaro Ishida, Jong Min Lim, Satoru Hiroto, Ko Furukawa, Dongho Kim, Takeaki Iwamoto, Hiroshi Shinokubo

Angewandte Chemie 126 巻 ( 6 ) 頁： 1532 - 1535 2014年1月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

<jats:title>Abstract</jats:title><jats:p>The treatment of an antiaromatic norcorrole Ni<jats:sup>II</jats:sup> complex with a kinetically stabilized silylene provided ring‐expansion products in excellent yields through the highly regio‐ and stereoselective insertion into the β‐β pyrrolic CC bonds. The resultant Ni<jats:sup>II</jats:sup> porphyrinoid monoinsertion product exhibited relatively strong near‐IR absorption bands due to the small HOMO–LUMO gap in spite of the disrupted cyclic π‐conjugation by the silicon atom.</jats:p>

DOI： 10.1002/ange.201309921

Transition metal catalyzed borylation of functional pi-systems 査読有り国際誌

Shinokubo Hiroshi

PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES 90 巻 ( 1 ) 頁： 1 - 11 2014年1月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：日本学士院

Borylated functional π-systems are useful building blocks to enable efficient synthesis of novel molecular architectures with beautiful structures, intriguing properties and unique functions. Introduction of boronic ester substituents to a variety of extended π-systems can be achieved through either iridium-catalyzed direct C–H borylation or the two-step procedure via electrophilic halogenation followed by palladium-catalyzed borylation. This review article focuses on our recent progress on borylation of large π-conjugated systems such as porphyrins, perylene bisimides, hexabenzocoronenes and dipyrrins.

DOI： 10.2183/pjab.90.1

Synthesis, reactivity and property of 5,15-dithiaporphyrin copper(II) complex 査読有り国際誌

Wachi Naruhiko, Kondo Takeshi, Ito Satoru, Hiroto Satoru, Shin Ji-Young, Shinokubo Hiroshi

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 18 巻 ( 8-9 ) 頁： 675 - 678 2014年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Porphyrins and Phthalocyanines

Preparation of 5,15-dithiaporphyrin copper(II) complex was carried out by treatment of 5,15-dithiaporphyrin free-base with copper(II) acetate. X-ray diffraction analysis elucidated its dimeric structure in the solid state, in which the meso-sulfur atom served as an axial ligand to each pentacoordinated Cu(II) center. Temperature dependent magnetic susceptibility of the complex was measured to reveal the weak antiferromagnetic interaction between two Cu(II) centers in the solid state. 5,15-dithiaporphyrin Cu(II) complex was converted into 10-thiacorrole Cu(II) complex in good yield upon heating with triphenylphosphine in refluxing toluene.

DOI： 10.1142/S1088424614500412

Oxidation of 2-amino-substituted BODIPYs providing pyrazine-fused BODIPY trimers 査読有り国際誌

Yokoi Hiroki, Wachi Naruhiko, Hiroto Satoru, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 50 巻 ( 21 ) 頁： 2715 - 2717 2014年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

Oxidation of 2-amino-substituted BODIPYs afforded BODIPY trimers in a one-step operation. The trimer consists of a pyrazine-fused BODIPY dimer to which one BODIPY unit is connected through an NH linkage. Effective expansion of π-conjugation over the fused dimer was observed in optical and electrochemical measurements. © 2014 Royal Society of Chemistry.

DOI： 10.1039/c3cc48738e

Selective Synthesis of a [32]Octaphyrin(1.0.1.0.1.0.1.0) Bis(palladium) Complex by a Metal-Templated Strategy 査読有り国際誌

Kido Hiromitsu, Shin Ji-Young, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 52 巻 ( 51 ) 頁： 13727 - 13730 2013年12月

Hiromitsu Kido, Ji‐Young Shin, Hiroshi Shinokubo

Angewandte Chemie 125 巻 ( 51 ) 頁： 13972 - 13975 2013年10月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

A shapely figure: A [32]octaphyrin(1.0.1.0.1.0.1.0) bis[palladium(II)] complex was selectively obtained through a metal-templated intermolecular homocoupling of a α,α'-dibromodipyrrin palladium(II) complex without formation the norcorrole. The weak antiaromatic character of the figure-eight [32]octaphyrin(1.0.1.0.1.0.1.0) system has been elucidated by spectroscopic measurements and DFT calculations.

DOI： 10.1002/ange.201306905

PubMed

Synthesis of Pyridine-Fused Perylene Imides with an Amidine Moiety for Hydrogen Bonding 査読有り国際誌

Ito Satoru, Hiroto Satoru, Shinokubo Hiroshi

ORGANIC LETTERS 15 巻 ( 12 ) 頁： 3110 - 3113 2013年6月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

Pyridine-fused perylene tetracarboxylic acid bisimides (PBIs) were synthesized via Suzuki-Miyaura coupling and acid condensation. The fused PBIs with electron-donating substituents exhibited an intramolecular charge transfer interaction. One of the N-alkyl substituents was selectively removed with BBr3 to create an amidine guest binding site. A hydrogen bonding interaction with pentafluorobenzoic acid changed the absorption spectra and enhanced fluorescence. © 2013 American Chemical Society.

DOI： 10.1021/ol401316q

Porphyrin Analogues That Consist of Indole, Benzofuran, and Benzothiophene Subunits 査読有り国際誌

Nakamura Shoichi, Kondo Takeshi, Hiroto Satoru, Shinokubo Hiroshi

ASIAN JOURNAL OF ORGANIC CHEMISTRY 2 巻 ( 4 ) 頁： 312 - 319 2013年4月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Asian Journal of Organic Chemistry

We have designed and synthesized porphyrin analogues that consist of benzofuran, benzothiophene, and indole subunits through iridium-catalyzed CH borylation of bisbenzoheterole precursors and subsequent palladium-catalyzed cross-couplings. In the case of the benzofuran derivatives, a cyclic hexamer was also obtained. The cyclic benzoheterole tetramers were more stable in air than the corresponding cyclic tetraindole. X-ray crystallography revealed that the benzoheterole tetramers have more planar conformations than the cyclic tetraindole. Compared with the cyclic tetraindole, the lowest energy bands in the absorption spectra of the cyclic benzoheteroles are red-shifted, which shows the effective expansion of π-conjugation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/ajoc.201300033

Functionalization of Hexa-peri-hexabenzocoronenes: Investigation of the Substituent Effects on a Superbenzene 査読有り国際誌

Yamaguchi Ryuichi, Ito Satoru, Lee Byung Sun, Hiroto Satoru, Kim Dongho, Shinokubo Hiroshi

CHEMISTRY-AN ASIAN JOURNAL 8 巻 ( 1 ) 頁： 178 - 190 2013年1月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - An Asian Journal

We have demonstrated that the iridium-catalyzed direct borylation of hexa-peri-hexabenzocoronene (HBC) enables regioselective introduction of boryl groups to the para-, ortho-, and meta-substituted HBCs in high yields. The boryl groups have been transformed into various functionalities such as hydroxy, cyano, ethynyl, and amino groups. We have elucidated that the substituents significantly influence the photophysical properties of HBCs to enhance fluorescence quantum yields. DFT calculations revealed that the origin of the substituent effect is the lift in degeneracy in the frontier orbitals by an interaction with electron-donating and electron-withdrawing substituents at the para- and ortho-positions. The change in molecular orbitals results in an increase of the transition probability from the S0→S1 states. In addition, the two-photon absorption cross-section values of para-substituted HBCs are significantly larger than those of ortho- and meta-substituted HBCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/asia.201200723

Synthesis of Highly Distorted pi-Extended [2.2]Metacyclophanes by Intermolecular Double Oxidative Coupling 査読有り国際誌

Koyama Yutaro, Hiroto Satoru, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 52 巻 ( 22 ) 頁： 5740 - 5743 2013年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

A strained relationship: Oxidation of dihydroxy-substituted acenes provides face-to-face [2.2]metacyclophane-like dimers (see scheme; Ored, Si of iPr 3Si groupsblue). The products exhibited highly distorted structures caused by steric repulsion. UV/Vis and electrochemical analysis revealed that the HOMO-LUMO gap was decreased upon dimerization. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201301180

Carbolithiation of meso-aryl-substituted 5,15-diazaporphyrin selectively provides 3-alkylated diazachlorins 査読有り国際誌

Yamaji Ayaka, Hiroto Satoru, Shin Ji-Young, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 49 巻 ( 44 ) 頁： 5064 - 5066 2013年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Communications

Treatment of meso-mesityl 5,15-diazaporphyrin with alkyllithiums in toluene at low temperature provided monoalkylated diazachlorins through highly regioselective nucleophilic addition at the β-position near the meso-nitrogen atom. © 2013 The Royal Society of Chemistry.

DOI： 10.1039/c3cc41907j

Assembled structures of dipyrrins and their oligomers bridged by dioxy-boron moieties 査読有り国際誌

Maeda Hiromitsu, Nishimura Yuki, Hiroto Satoru, Shinokubo Hiroshi

DALTON TRANSACTIONS 42 巻 ( 45 ) 頁： 15885 - 15888 2013年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Dalton Transactions

A linear arrangement of BODIPY dimers and trimers was transformed into boron-bridged box, ladder and cage structures on treatment with spacer units possessing multiple diol moieties. © 2013 The Royal Society of Chemistry.

DOI： 10.1039/c3dt50783a

meso-Thiaporphyrinoids Revisited: Missing of Sulfur by Small Metals 査読有り国際誌

Kamiya Hiroki, Kondo Takeshi, Sakida Takafumi, Yamaguchi Shigeru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 18 巻 ( 50 ) 頁： 16129 - 16135 2012年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

Facile synthesis of meso-aryl-substituted 5,15-dithiaporphyrins and 10-thiacorroles has been achieved by sulfidation of α,α'- dichlorodipyrrin metal complexes with sodium sulfide in DMF. Thiacorrole metal complexes exhibit distinct aromaticity due to 18 π-conjugation including the lone pair on sulfur, whereas dithiaporphyrins are nonaromatic judging from 1H NMR spectra, X-ray analysis, and absorption spectra. We have found that NiII and AlIII dithiaporphyrin complexes undergo smooth thermal sulfur extrusion reaction to give the corresponding thiacorrole complexes, whereas free base, ZnII, PdII, and Pt II dithiaporphyrin complexes did not exhibit the similar reactivity. The DFT calculations have elucidated a reaction pathway involving an episulfide intermediate, which can explain the markedly different reactivity among dithiaporphyrin metal complexes. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/chem.201203255

Synthesis of Oxygen-Substituted Hexa-peri-hexabenzocoronenes through Ir-Catalyzed Direct Borylation 査読有り国際誌

Yamaguchi Ryuichi, Hiroto Satoru, Shinokubo Hiroshi

ORGANIC LETTERS 14 巻 ( 10 ) 頁： 2472 - 2475 2012年5月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

Direct C-H borylation of hexa-peri-hexabenzocoronenes (HBCs) has been achieved under iridium catalysis, which allows efficient synthesis of hydroxy-substituted HBCs by oxidation of the boryl groups. Further oxidation of dihydroxy HBC with phenyliodine bis(trifluoroacetate) (PIFA) afforded tetraoxo-substituted HBC without any regioisomers, which can be considered as a π-extended quinone. © 2012 American Chemical Society.

DOI： 10.1021/ol300743f

Synthesis of Nickel(II) Azacorroles by Pd-Catalyzed Amination of a,a'-Dichlorodipyrrin NiII Complex and Their Properties 査読有り国際誌

Horie Miki, Hayashi Yosuke, Yamaguchi Shigeru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL 18 巻 ( 19 ) 頁： 5919 - 5923 2012年5月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry - A European Journal

Synthesis of nickel(II) complexes of meso-aryl-substituted azacorroles was performed by Buchwald-Hartwig amination of a dipyrrin Ni II complex with benzylamine through C-N and C-C coupling. The highly planar structure of Ni II azacorroles was elucidated by X-ray diffraction analysis. 1H NMR analysis and nucleus independent chemical shift (NICS) calculation on Ni II azacorrole revealed its distinct aromaticity with [17]triaza-annulene 18π conjugation. In addition, acylation of azacorrole selectively afforded N- and C-acylated azacorroles depending on the reaction conditions, showing the dual reactivity of azacorroles. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/chem.201200485

Energy and Electron Transfer from Fluorescent Mesostructured Organosilica Framework to Guest Dyes 査読有り国際誌

Mizoshita Norihiro, Yamanaka Ken-ichi, Hiroto Satoru, Shinokubo Hiroshi, Tani Takao, Inagaki Shinji

LANGMUIR 28 巻 ( 8 ) 頁： 3987 - 3994 2012年2月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

Energy and electron transfer from frameworks of nanoporous or mesostructured materials to guest species in the nanochannels have been attracting much attention because of their increasing availability for the design and construction of solid photofunctional systems, such as luminescent materials, photovoltaic devices, and photocatalysts. In the present study, energy and electron-transfer behavior of dye-doped periodic mesostructured organosilica films with different host-guest arrangements were systematically examined. Fluorescent tetraphenylpyrene (TPPy)-silica mesostructured films were used as a host donor. The location of guest perylene bisimide (PBI) dye molecules, acting as an acceptor, could be controlled on the basis of the molecular design of the PBI substituent groups. PBI dyes with bulky substituents and polar anchoring groups were located at the pore surface with low self-aggregation, which induced efficient energy or electron transfer because of the close host-guest arrangement. However, PBI dye with bulky and hydrophobic substituents was located in the center of template surfactant micelles; the fluorescence emission from the host TPPy groups was hardly quenched when the host-guest distance was longer than the critical Förster radius (ca. 4.5 nm). The relationship between the energy or electron-transfer efficiency and the location of guest species in the channels of mesostructured organosilica was first revealed by molecular design of the PBI substituents. © 2012 American Chemical Society.

DOI： 10.1021/la204645k

Facile Synthesis of Biphenyl-Fused BODIPY and Its Property 査読有り国際誌

Hayashi Yosuke, Obata Naoki, Tamaru Masatomo, Yamaguchi Shigeru, Matsuo Yutaka, Saeki Akinori, Seki Shu, Kureishi Yuka, Saito Shohei, Yamaguchi Shigehiro, Shinokubo Hiroshi

ORGANIC LETTERS 14 巻 ( 3 ) 頁： 866 - 869 2012年2月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the β-position of the BODIPY unit. The extended π-system of the fused BODIPY induces near-infrared (NIR) absorption and strong π - π interactions in the solid state. These features are beneficial for the application of the dye as a functional material. The biphenyl-fused BODIPY dye was demonstrated to exhibit photocurrent conversion ability on the basis of its n-type semiconducting property. © 2012 American Chemical Society.

DOI： 10.1021/ol2033916

Ensemble and Single-Molecule Spectroscopic Study on Excitation Energy Transfer Processes in 1,3-Phenylene-Linked Perylenebisimide Oligomers 査読有り国際誌

Bahng Hee Won, Yoon Min-Chul, Lee Ji-Eun, Murase Yuichi, Yoneda Tomoki, Shinokubo Hiroshi, Osuka Atsuhiro, Kim Dongho

JOURNAL OF PHYSICAL CHEMISTRY B 116 巻 ( 4 ) 頁： 1244 - 1255 2012年2月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

1,3-Phenylene-bridged perylenebisimide dimer (PBI2) and trimer (PBI3) were prepared along with monomer reference (PBI1) using perylene imide-anhydride 5 as a key precursor. 3,3-Dimethylbut-1-yl substituents were introduced at the 2,5-positions of perylenebisimide (PBI) to improve the solubilities of PBI oligomers. Actually, no serious aggregation of PBI2 and PBI3 was detected in their dilute CH2Cl2 solutions. Under these conditions, intramolecular electronic interactions among PBI chromophores have been revealed by measuring the photophysical properties at their ensemble and single-molecule levels. The excitation energy transfer times of PBI2 (0.16 ps) and PBI3 (0.60 ps) were determined from the two different observables, anisotropy depolarization, and singlet-singlet annihilation, respectively, which are considered as the incoherent Förster-type energy hopping (EEH) times as compared with the EEH time constant (1.97 ps) calculated on the basis of the Förster mechanism. The relatively short EEH times compared to similar PBI oligomers can be attributed to 1,3-phenylene linker, which assures a short distance between the chromophores and, as a consequence, makes it hard to treat the PBI unit as a point dipole. The limitation of point-dipole approximation to describe the PBI oligomers and additional through-bond type interactions can be attributed as the causes of the discrepancies in excitation energy transfer times. Considering these photophysical properties, we can suggest that 1,3-phenylene-linked PBI oligomers have potentials as molecular photonic devices including the artificial light-harvesting system. © 2011 American Chemical Society.

DOI： 10.1021/jp208855u

Synthesis and oxidation of cyclic tetraindole 査読有り国際誌

Nakamura Shoichi, Hiroto Satoru, Shinokubo Hiroshi

CHEMICAL SCIENCE 3 巻 ( 2 ) 頁： 524 - 527 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Science

A cyclic indole tetramer has been synthesized via an iridium-catalysed C-H borylation-cross coupling sequence. The tetraindole has a highly distorted structure, but can be oxidized with bromine and water into a highly planar macrocycle. The oxidized macrocycle can capture metal ions in its inner cavity as a novel porphyrin analogue, accompanied by a significant colour change from purple to blue or black. © 2012 The Royal Society of Chemistry.

DOI： 10.1039/c1sc00665g

Mesoporous Organosilica Hybrids Consisting of Silica-Wrapped p-p Stacking Columns 査読有り国際誌

Mizoshita Norihiro, Tani Takao, Shinokubo Hiroshi, Inagaki Shinji

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 巻 ( 5 ) 頁： 1156 - 1160 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

A new class of periodic mesoporous organosilica (PMO) materials with a columnar π-stacking arrangement of the framework organic groups has been prepared from disklike precursors with hydrophobic perylene bisimide (PBI) cores (see picture). The PBI-bridged PMOs exhibit exciton coupling and efficient formation of mobile radical spins by electron doping within the pore walls. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201105394

A meso-Spiro[Cyclopentadiene-Isoporphyrin] from a Phenylethynyl Porphyrin Platinum(II) Pincer Complex 査読有り国際誌

Anabuki Shoma, Shinokubo Hiroshi, Aratani Naoki, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 巻 ( 13 ) 頁： 3174 - 3177 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

A good catch: The oxidation of a phenylethynyl Pt II pincer complex with iodine led to formal reductive elimination but without the liberation of Pt II, which was caught by the 2-pyridyl substituents on the Ni II porphyrin. The unique reactivity of the Pt II pincer complex led to the formation of a meso-spiro[cyclopentadiene- isoporphyrin]. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201109091

Oxidative Annulation of ss-Aminoporphyrins into Pyrazine-Fused Diporphyrins 査読有り国際誌

Akita Masanari, Hiroto Satoru, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 巻 ( 12 ) 頁： 2894 - 2897 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Dimers are a girl's best friend: The oxidative fusion reaction of β-aminoporphyrins with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under high-dilution conditions furnishes pyrazine-fused diporphyrins 1 in high yields. In a further application of the reaction, the oxidation of a 5,10,15,20-tetraphenylporphyrin derivative provides a singly linked diaminodiporphyrin 2 along with the pyrazine-fused diporphyrin (see scheme; only core structures are shown). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201108037

Gram-Scale Synthesis of Nickel(II) Norcorrole: The Smallest Antiaromatic Porphyrinoid 査読有り国際誌

Ito Tomohiro, Hayashi Yosuke, Shimizu Soji, Shin Ji-Young, Kobayashi Nagao, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 巻 ( 34 ) 頁： 8542 - 8545 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

Small is beautiful: A ring-contracted sister of porphyrin, norcorrole, has been synthesized efficiently as a stable molecule by a nickel-templated strategy. The norcorrole complex is stable but exhibits a distinct antiaromatic character according to the Hückel rule. Oxidation of the norcorrole complex provides an aromatic oxacorrole complex.

DOI： 10.1002/anie.201204395

Intermolecular Oxidative Annulation of 2-Aminoanthracenes to Diazaacenes and Aza[7]helicenes 査読有り国際誌

Goto Kiyohiko, Yamaguchi Ryuichi, Hiroto Satoru, Ueno Hiroshi, Kawai Tsuyoshi, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 巻 ( 41 ) 頁： 10333 - 10336 2012年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Which way to go: The product distribution in the efficient oxidation of 2-aminoanthracene derivatives to pyrazine- and pyrrole-fused bisanthracenes can be controlled by additives (see scheme; TFA=trifluoroacetic acid, DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The pyrrole-fused dimer can be regarded as an aza[7]helicene with a stable helical conformation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201204863

Functionalization of a Simple Dithienylethene via Palladium-Catalyzed Regioselective Direct Arylation 査読有り国際誌

Kamiya Hiroki, Yanagisawa Shuichi, Hiroto Satoru, Itami Kenichiro, Shinokubo Hiroshi

ORGANIC LETTERS 13 巻 ( 24 ) 頁： 6394 - 6397 2011年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society (ACS)

The direct arylation on the thienyl groups of a diarylethene with various aryl iodides efficiently provided arylated dithienylethenes under palladium catalysis. Unsymmetrically substituted dithienylethenes were also synthesized by this protocol. This procedure allows a rapid access to a variety of aryl-substituted dithienylethenes from a single substrate of a simple dithienylethene. © 2011 American Chemical Society.

DOI： 10.1021/ol2026069

A Hexameric Porphyrin Triangle Constructed by Suzuki-Miyaura Cross-coupling Reaction 査読有り国際誌

Song Jianxin, Anabuki Shoma, Aratani Naoki, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY LETTERS 40 巻 ( 9 ) 頁： 902 - 903 2011年9月

Synthetic Protocol for Diarylethenes through Suzuki-Miyaura Coupling 査読有り

Satoru Hiroto, Katsuya Suzuki, Hiroki Kamiya, and Hiroshi Shinokubo

Chem. Commun. 47 巻 ( 25 ) 頁： 7149-7151 2011年5月

Synthesis of Directly Connected BODIPY Oligomers through Suzuki-Miyaura Coupling 査読有り

Yosuke Hayashi, Shigeru Yamaguchi, Won Young Cha, Dongho Kim, and Hiroshi Shinokubo

Org. Lett. 13 巻 ( 12 ) 頁： 2992-2995 2011年5月

Iridium-Catalyzed Direct Tetraborylation of Perylene Bisimides 査読有り

Takuro Teraoka, Satoru Hiroto, and Hiroshi Shinokubo

Org. Lett. 13 巻 ( 10 ) 頁： 2532-2535 2011年4月

Metal-Mediated Synthesis of Antiaromatic Porphyrinoids from a BODIPY Precursor 査読有り

Takafumi Sakida, Shigeru Yamaguchi, and Hiroshi Shinokubo

Angew. Chem., Int. Ed. 50 巻 ( 10 ) 頁： 2280-2283 2011年2月

A beta-to-beta 2,5-Thienylene-Bridged Cyclic Porphyrin Tetramer: Its Rational Synthesis and 1:2 Binding Mode with C60 査読有り

Jianxin Song, Naoki Aratani, Hiroshi Shinokubo, and Atsuhiro Osuka

Chem. Sci. 2 巻 ( 4 ) 頁： 748-751 2011年1月

Peripherally Cyclometalated Iridium Complexes of Dipyridylporphyrin 査読有り

Keita Yoshida, Takumi Nakashima, Shigeru Yamaguchi, Atsuhiro Osuka and Hiroshi Shinokubo

Dalton Trans. 頁： in press 2011年

Synthesis of a Diimidazolylporphyrin Pincer Palladium Complex 査読有り

Jun Yamamoto, Tomohiro Shimizu, Shigeru Yamaguchi, Naoki Aratani, Hiroshi Shinokubo and Atsuhiro Osuka

J. Porphyrins Phthalocyanines 頁： in press 2011年

Pyrrole-Bridged Porphyrin Nanorings 査読有り

Jianxin Song, Naoki Aratani, and Hiroshi Shinokubo, Atsuhiro Osuka

Chem. Eur. J. 16 巻 ( 45 ) 頁： 13320-13324 2010年11月

A Porphyrin Nanobarrel that Encapsulates C60 査読有り

Jianxin Song, Naoki Aratani, Hiroshi Shinokubo, and Atsuhiro Osuka

J. Am. Chem. Soc. 132 巻 ( 46 ) 頁： 16356-16357 2010年10月

Platinum(II) and Platinum(IV) Porphyrin Pincer Complexes: Synthesis, Structures, and Reactivity 査読有り国際誌

Yoshida Keita, Yamaguchi Shigeru, Osuka Atsuhiro, Shinokubo Hiroshi

ORGANOMETALLICS 29 巻 ( 17 ) 頁： 3997 - 4000 2010年9月

Directly Pd(II)-Bridged Porphyrin Belts with Remarkable Curvatures 査読有り

Jianxin Song, Naoki Aratani, Ji Haeng Heo, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

J. Am. Chem. Soc. 132 巻 ( 34 ) 頁： 11868-11869 2010年9月

eta(2)-Porphyrin Ru(II) pi Complexes 査読有り国際誌

Yamaguchi Shigeru, Shinokubo Hiroshi, Osuka Atsuhiro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132 巻 ( 29 ) 頁： 9992 - 9993 2010年7月

A Stable Non-Kekule Singlet Biradicaloid from meso-Free 5,10,20,25-Tetrakis(Pentafluorophenyl)-Substituted [26]Hexaphyrin(1.1.1.1.1.1) 査読有り国際誌

Koide Taro, Furukawa Ko, Shinokubo Hiroshi, Shin Jae-Yoon, Kim Kil Suk, Kim Dongho, Osuka Atsuhiro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132 巻 ( 21 ) 頁： 7246 - + 2010年6月

Synthesis of meso,meso'-Pyrrole-Bridged Diporphyrins by Cu(I)-Mediated Annulation 査読有り

Chihiro Maeda, Hiroshi Shinokubo, and Atsuhiro Osuka

Org. Lett. 12 巻 ( 8 ) 頁： 1820-1823 2010年4月

Porphyrin "Lego Block" Strategy To Construct Directly meso-beta Doubly Linked Porphyrin Rings 査読有り

Jianxin Song, Naoki Aratani, Pyosang Kim, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Angew. Chem., Int. Ed. 49 巻 ( 21 ) 頁： 3617-3620 2010年4月

Large Porphyrin Squares from the Self-Assembly of meso-Triazole-Appended L-Shaped meso-meso-Linked ZnII-Triporphyrins: Synthesis and Efficient Energy Transfer 査読有り

Chihiro Maeda, Pyosang Kim, Sung Cho, Jong Kang Park, Jong Min Lim, Dongho Kim, Josh Vura-Weis, Michael R. Wasielewski, and Hiroshi Shinokubo, Atsuhiro Osuka

Chem. Eur. J. 16 巻 ( 17 ) 頁： 5052-5061 2010年3月

Excess Polarizability Reveals Exciton Localization/Delocalization Controlled by Linking Positions on Porphyrin Rings in Butadiyne-Bridged Porphyrin Dimers 査読有り

Chunxing She, Shanmugam Easwaramoorthi, Pyosang Kim, Satoru Hiroto, Ichiro Hisaki, Hiroshi Shinokubo, Atsuhiro Osuka, Dongho Kim and Joseph T. Hupp

J. Phys. Chem. A 114 巻 ( 10 ) 頁： 3384-3390 2010年3月

Strategic Synthesis of 2,6-Pyridylene-Bridged β-to-β Porphyrin Nanorings through Cross-Coupling 査読有り

Jianxin Song, Pyosang Kim, Naoki Aratani, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Chem. Eur. J. 16 巻 ( 10 ) 頁： 3009-3012 2010年2月

Bithiophene-Porphyrin Hybrid Nanorings 査読有り

Kenta Osawa, Jianxin Song, Ko Furukawa, Hiroshi Shinokubo, Naoki Aratani, and Atsuhiro Osuka

Chem. Asian J. 5 巻 ( 4 ) 頁： 764-767 2010年1月

A Stable Organic Radical Delocalized on a Highly Twisted pi System Formed Upon Palladium Metalation of a Mobius Aromatic Hexaphyrin 査読有り国際誌

Rath Harapriya, Tokuji Sumito, Aratani Naoki, Furukawa Ko, Lim Jong Min, Kim Dongho, Shinokubo Hiroshi, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 巻 ( 8 ) 頁： 1489 - 1491 2010年

Doubly beta-Functionalized Meso-Meso Directly Linked Porphyrin Dimer Sensitizers for Photovoltaics 査読有り国際誌

Park Jong Kang, Chen Jinping, Lee Hye Ryun, Park Sun Woo, Shinokubo Hiroshi, Osuka Atsuhiro, Kim Dongho

JOURNAL OF PHYSICAL CHEMISTRY C 113 巻 ( 52 ) 頁： 21956 - 21963 2009年12月

Synthesis of Arylated Perylene Bisimides through C-H Bond Cleavage under Ruthenium Catalysis 査読有り

Satomi Nakazono, Shanmugam Easwaramoorthi, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Org. Lett. 11 巻 ( 23 ) 頁： 5426-5429 2009年12月

meso,meso '-Bis(5-azaindol-2-yl)-Appended meso-meso-Linked Zn(II) Diporphyrin: A Discrete Fluorescent Assembly 査読有り国際誌

Maeda Chihiro, Shinokubo Hiroshi, Osuka Atsuhiro

ORGANIC LETTERS 11 巻 ( 22 ) 頁： 5322 - 5325 2009年11月

Palladium-Catalyzed Dimerization of meso-Bromoporphyrins: Highly Regioselective meso-beta Coupling through Unprecedented Remote C-H Bond Cleavage 査読有り国際誌

Tokuji Sumito, Yurino Taiga, Aratani Naoki, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY-A EUROPEAN JOURNAL 15 巻 ( 45 ) 頁： 12208 - 12211 2009年10月

Regioselective Ru-Catalyzed Direct 2,5,8,11-Alkylation of Perylene Bisimides 査読有り

Satomi Nakazono, Yusuke Imazaki, Hyejin Yoo, Jaesung Yang, Takahiro Sasamori, Norihiro Tokitoh, Tassel Cédric, Hiroshi Kageyama, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Chem. Eur. J. 15 巻 ( 31 ) 頁： 7530-7533 2009年7月

炭素ー金属結合をもつポルフィリン系化合物査読有り

廣戸　聡、山口　滋、忍久保　洋、大須賀　篤弘

有機合成化学協会誌 67 巻 ( 7 ) 頁： 688-700 2009年7月

Unusual Interchromophoric Interactions in beta,beta ' Directly and Doubly Linked Corrole Dimers: Prohibited Electronic Communication and Abnormal Singlet Ground States 査読有り国際誌

Cho Sung, Lim Jong Min, Hiroto Satoru, Kim Pyosang, Shinokubo Hiroshi, Osuka Atsuhiro, Kim Dongho

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 131 巻 ( 18 ) 頁： 6412 - 6420 2009年5月

Bis-rhodium hexaphyrins: metalation of [28]hexaphyrin and a smooth Huckel aromatic-antiaromatic interconversion 査読有り国際誌

Rath Harapriya, Aratani Naoki, Lim Jong Min, Lee Jae Seok, Kim Dongho, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMICAL COMMUNICATIONS ( 25 ) 頁： 3762 - 3764 2009年5月

Functionalization of Boron Dipyrrin (BODIPY) Dyes through Iridium and Rhodium Catalysis: A Complementary Approach to alpha- and beta-Substituted BODIPYs 査読有り国際誌

Chen Jinping, Mizumura Masatoshi, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY-A EUROPEAN JOURNAL 15 巻 ( 24 ) 頁： 5942 - 5949 2009年5月

Metathesis-like Splitting Reactions of Metallated [36]Octaphyrins(1.1.1.1.1.1.1.1): Experimental and Computational Investigations 査読有り国際誌

Tanaka Yasuo, Shinokubo Hiroshi, Yoshimura Yosuke, Osuka Atsuhiro

CHEMISTRY-A EUROPEAN JOURNAL 15 巻 ( 23 ) 頁： 5674 - 5685 2009年4月

Conformational Changes of meso-Aryl Substituted Expanded Porphyrins upon Protonation: Effects on Photophysical Properties and Aromaticity 査読有り

Jae-Yoon Shin, Jong Min Lim, Zin Seok Yoon, Kil Suk Kim, Min-Chul Yoon, Satoru Hiroto, Hiroshi Shinokubo, Soji Shimizu, Atsuhiro Osuka, and Dongho Kim

J. Phys. Chem. B, 113 巻 ( 17 ) 頁： 5794–5802 2009年4月

Post-Modification of meso-meso-Linked Porphyrin Arrays by Iridium and Rhodium Catalyses for Tuning of Energy Gap 査読有り国際誌

Chen Jinping, Aratani Naoki, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY-AN ASIAN JOURNAL 4 巻 ( 7 ) 頁： 1126 - 1133 2009年3月

First self-assembly study of large pi-conjugated corrole dimers on solid substrates 査読有り国際誌

Miao Xinrui, Gao Aimei, Li Zhuomin, Hiroto Satoru, Shinokubo Hiroshi, Osuka Atsuhiro, Deng Wenli

APPLIED SURFACE SCIENCE 255 巻 ( 11 ) 頁： 5885 - 5890 2009年3月

Adsorption characteristic of self-assembled corrole dimers on HOPG 査読有り国際共著国際誌

Miao, XR; Gao, AM; Hiroto, S; Shinokubo, H; Osuka, A; Xin, HL; Deng, WL

SURFACE AND INTERFACE ANALYSIS 41 巻 ( 3 ) 頁： 225 - 230 2009年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

<jats:title>Abstract</jats:title><jats:p>Our study first focus on two types of corrole dimers oxidized and reduced forms on highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) and contact angle measurement (CAM) were used to investigate the self‐assembled monolayers of corrole dimers adsorbed on HOPG surfaces at room temperature in air. XPS and CAM results have confirmed both two molecules adsorbed on an HOPG surface and formed self‐assembled films, and STM experiments found that the corrole dimers adsorbed on HOPG surfaces form similar lobes. The different stable space structure of the oxidized form molecule (OFM) and reduced form molecule (RFM), led to the diversity of the tetramer structural dimensions. The occurrence of molecular aggregations and assembly was controlled by the interactions between molecular–molecular and molecule–substrate. The electrostatic interactions between the molecules control the geometrical sizes and molecule–substrate interactions determine topographical shapes of the self‐assembled corrole dimers on HOPG surface. Copyright © 2009 John Wiley & Sons, Ltd.</jats:p>

DOI： 10.1002/sia.3011

Zwitterionic Corroles: Regioselective Nucleophilic Pyridination of a Doubly Linked Biscorrole 査読有り国際誌

Hiroto Satoru, Aratani Naoki, Shibata Naoki, Higuchi Yoshiki, Sasamori Takahiro, Tokitoh Norihiro, Shinokubo Hiroshi, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 48 巻 ( 13 ) 頁： 2388 - 2390 2009年2月

Double Cleavage of sp(2) C-H and sp(3) C-H Bonds on One Metal Center: DMF-Appended Cyclometalated Platinum(II) and -(IV) Porphyrins 査読有り国際誌

Yamaguchi Shigeru, Shinokubo Hiroshi, Osuka Atsuhiro

INORGANIC CHEMISTRY 48 巻 ( 3 ) 頁： 795 - 797 2009年2月

Adsorption Characteristic of Self-Assembled Corrole Dimers on HOPG 査読有り

Xinrui Miao, Aimei Gao, Satoru Hiroto, Hiroshi Shinokubo, Atsuhiro Osuka, Hongliang Xina, and Wenli Deng

Surf. Interface Anal. 41 巻頁： 225–230 2009年1月

Synthesis of Norbornane-Bridged Diporphyrins via Palladium-Catalyzed [3+2] Annulation Strategy 査読有り国際誌

Mizumura Masatoshi, Shinokubo Hiroshi, Osuka Atsuhiro

SYNTHESIS-STUTTGART ( 1 ) 頁： 59 - 61 2009年1月

Marriage of porphyrin chemistry with metal-catalysed reactions 査読有り国際誌

Shinokubo Hiroshi, Osuka Atsuhiro

CHEMICAL COMMUNICATIONS ( 9 ) 頁： 1011 - 1021 2009年

Synthesis of a pyridine-fused porphyrinoid: oxopyridochlorin 査読有り国際誌

Tokuji Sumito, Takahashi Yuji, Shinmori Hideyuki, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMICAL COMMUNICATIONS ( 9 ) 頁： 1028 - 1030 2009年

ビチオフェンにより架橋された環状ポルフィリン多量体の合成査読有り国際誌

大澤健太, 宗建新, 荒谷直樹, 忍久保洋, 大須賀篤弘

基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集） 2009 巻 ( 0 ) 頁： 242 - 242 2009年

担当区分：責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：基礎有機化学会（基礎有機化学連合討論会）

これまで報告されている環状ポルフィリン多量体は、そのほとんどがエチニル基やフェニル基など、炭素骨格の架橋分子を用いていた。そこで今回、機能性有機分子であるビチオフェンにより架橋された環状ポルフィリン多量体の合成を試みた。実際に５，１０－ジブロモポルフィリンと５，５’－ジホウ素化ビチオフェンを用いて鈴木ー宮浦カップリングを行った所、ビチオフェン架橋環状ポルフィリン３～５量体を、いずれも約５％の収率で合成する事に成功した。当日の発表では、構造の同定、及び物性についてもあわせて報告する。

DOI： 10.11494/kisoyuki.2009.0.242.0

Synthesis of Directly and Doubly Linked Dioxoisobacteriochlorin Dimers 査読有り国際誌

Hiroto Satoru, Hisaki Ichiro, Shinokubo Hiroshi, Osuka Atsuhiro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 巻 ( 48 ) 頁： 16172 - 16173 2008年12月

Pt(II)- and Pt(IV)-Bridged Cofacial Diporphyrins via Carbon-Transition Metal sigma-Bonds 査読有り国際誌

Yamaguchi Shigeru, Katoh Taisuke, Shinokubo Hiroshi, Osuka Atsuhiro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 巻 ( 44 ) 頁： 14440 - + 2008年11月

Unambiguous identification of Mobius aromaticity for meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) 査読有り国際誌

Sankar Jeyaraman, Mori Shigeki, Saito Shohei, Rath Harapriya, Suzuki Masaaki, Inokuma Yasuhide, Shinokubo Hiroshi, Kim Kil Suk, Yoon Zin Seok, Shin Jae-Yoon, Lim Jong Min, Matsuzaki Yoichi, Matsushita Osamu, Muranaka Atsuya, Kobayashi Nagao, Kim Dongho, Osuka Atsuhiro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 巻 ( 41 ) 頁： 13568 - 13579 2008年10月

Photoelectrochemical Properties of Doubly beta-Functionalized Porphyrin Sensitizers for Dye-Sensitized Nanocrystalline-TiO2 Solar Cells 査読有り国際誌

Park Jong Kang, Lee Hye Ryun, Chen Jinping, Shinokubo Hiroshi, Osuka Atsuhiro, Kim Dongho

JOURNAL OF PHYSICAL CHEMISTRY C 112 巻 ( 42 ) 頁： 16691 - 16699 2008年10月

2,5-Thienylene-Bridged Triangular and Linear Porphyrin Trimers 査読有り

Jianxin Song, So Young Jang, Shigeru Yamaguchi, Jeyaraman Sankar, Satoru Hiroto, Naoki Aratani, Jae-Yoon Shin, Shanmugam Easwaramoorthi, Kil Suk Kim, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Angew. Chem., Int. Ed. 47 巻頁： 6004-6007 2008年7月

Synthesis of Novel Chiral Porphyrins through Pd-Catalyzed [3 + 2] Annulation and Heterochiral Self-Assembling to Form Heterodimers 査読有り

Masatoshi Mizumura, Hiroshi Shinokubo, and Atsuhiro Osuka

Angew. Chem., Int. Ed. 47 巻頁： 5387-5381 2008年6月

Highly selective Ir-catalyzed direct sixfold borylation of peripheral aromatic substituents on hexakisaryl-substituted [28]hexaphyrin(1.1.1.1.1.1) 査読有り国際誌

Mori Goro, Shinokubo Hiroshi, Osuka Atsuhiro

TETRAHEDRON LETTERS 49 巻 ( 13 ) 頁： 2170 - 2172 2008年3月

Highly selective Ir-catalyzed direct sixfold borylation of peripheral aromatic substituents on hexakisaryl-substituted [28]hexaphyrin(1.1.1.1.1.1) 査読有り国際誌

Mori Goro, Shinokubo Hiroshi, Osuka Atsuhiro

Tetrahedron Letters 49 巻 ( 13 ) 頁： 2170 - 2172 2008年3月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by iridium-catalyzed borylation with theSmith–Miyaura–Hartwig protocol. High para selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenylsubstituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrinwithout borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylatedhexaphyrin can be used for Suzuki–Miyaura cross coupling reaction.

Dimeric assemblies from 1 2,3-triazole-appended Zn(II) porphyrins with control of NH-tautomerism in 1 2,3-triazole 査読有り国際誌

Maeda Chihiro, Yamaguchi Shigeru, Ikeda Chusaku, Shinokubo Hiroshi, Osuka Atsuhiro

ORGANIC LETTERS 10 巻 ( 4 ) 頁： 549 - 552 2008年2月

meso-Aryl Substituted Rubyrin and Its Higher Homologues: Structural Characterization and Chemical Properties 査読有り

Soji Shimizu, Shohei Saito, Won-Seob Cho, Jonathan L. Sessler, Hiroshi Shinokubo, and Atsuhiro Osuka

Chem. Eur. J. 14 巻 ( 9 ) 頁： 2668-2678 2008年2月

Efficient Rhodium-Catalyzed installation of unsaturated ester functions onto porphyirins: Site-specific heck-type addition versus conjugate addition 査読有り国際誌

Baba Hiromi, Chen Jinping, Shinokubo Hiroshi, Osuka Atsuhiro

CHEMISTRY-A EUROPEAN JOURNAL 14 巻 ( 14 ) 頁： 4256 - 4262 2008年

Metalation of expanded porphyrins: A chemical trigger used to produce molecular twisting and Mobius aromaticity 査読有り国際誌

Tanaka Yasuo, Saito Shohei, Mori Shigeki, Aratani Naoki, Shinokubo Hiroshi, Shibata Naoki, Higuchi Yoshiki, Yoon Zin Seok, Kim Kil Suk, Noh Su Bum, Park Jong Kang, Kim Dongho, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 巻 ( 4 ) 頁： 681 - 684 2008年

Synthesis of chiral porphyrins through Pd-catalyzed [3+2] annulation and heterochiral self-assembly 査読有り国際誌

Mizumura Masatoshi, Shinokubo Hiroshi, Osuka Atsuhiro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 巻 ( 29 ) 頁： 5378 - 5381 2008年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

Positive discrimination: Palladium-catalyzed [3+2] annulation of meso-bromoporphyrin with norbornene derivatives efficiently provides novel chiral meso, b-fused porphyrins with a rigid structure (as shown). A chiral benzoazanorbornene-fused zinc porphyrin assembles selectively to form the slipped cofacial dimer in a heterochiral association, which allows construction of a heterodimer from two porphyrin components through chiral discrimination. (Chemical Equation Presented) © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/anie.200801269

Unambiguous Identification of Mobius Aromaticity for meso-Aryl-Substituted [28]Hexaphyrins (1. 1. 1. 1. 1. 1) 査読有り国際誌

忍久保洋

J. Am Chem. Soc. 130 頁： 13568 - 13579 2008年

ピリジンが縮環したポルフィリンの合成と性質査読有り国際誌

徳地澄人, 忍久保洋, 大須賀篤弘

基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集） 2008 巻 ( 0 ) 頁： 51 - 51 2008年

担当区分：責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：基礎有機化学会（基礎有機化学連合討論会）

縮環によるポルフィリンの共役系の拡張はその光学的特性および電気的特性の変化が期待でき興味深い。当研究室では、パラジウム触媒を用いてmeso-ブロモポルフィリンからデヒドロパープリンを合成することに成功し、さらにその酸化的開裂により3,5-ジベンゾイルポルフィリンが生成することを既に報告した。今回その3,5-ジベンゾイルポルフィリンを酢酸アンモニウムと反応させることにより、ピリジンを縮環したポルフィリンを合成することに成功した。この化合物は外骨格に窒素原子とカルボニル基を有する。そのＸ線結晶構造解析により判明した構造及び光物性を報告する。

DOI： 10.11494/kisoyuki.2008.0.51.0