受賞国：日本国

受賞国：日本国

受賞国：日本国

受賞国：日本国

受賞国：日本国

受賞国：日本国

受賞国：日本国

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

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

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  

Norcorrole derivatives with 3,4,5-trialkoxyphenyl moieties at the meso positions were synthesized to form various stacking assemblies in single crystals and thermotropic liquid crystals (LCs) depending on aliphatic chain lengths. Triple-decker stacking structures were formed via the interactions between the antiaromatic systems formed for the butoxy and dodecyloxy derivatives in the single-crystal and LC states, respectively. In particular, the LC state exhibited discotic columnar structures comprising triple deckers to exhibit high electric conductivity, as supported by molecular dynamics simulations.

DOI： 10.1039/d4sc01633e

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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

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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

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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  

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

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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：Journal of Materials Chemistry C  

Elucidation of intermolecular interactions is essential for understanding charge transport properties in organic materials and organic electronic devices. While interactions between aromatic molecules have been extensively studied, little is known about interactions between antiaromatic molecules. Theoretical considerations predict that when two antiaromatic porphyrin molecules are superimposed, the antiaromatic molecules should be stabilized by attractive intermolecular interactions. In this study, we used atomic force microscopy to evaluate intermolecular interactions originating from the π-π stacking of the two antiaromatic porphyrin moieties at the molecular level. We evaluated substantial interaction between the antiaromatic porphyrin moieties as an adhesion force of the antiaromatic porphyrin molecular pairs using force spectroscopy. The present result supports the formation of π-π stacking due to the attractive interaction between the two antiaromatic π-systems at the single-molecule level.

DOI： 10.1039/d3tc04166b

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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：Journal of Physical Chemistry Letters  

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

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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  

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.

DOI： 10.1093/chemle/upad015

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

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  

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

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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  

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 a distinct antiaromatic character due to its highly planar conformation. Detailed density functional theory (DFT) calculations revealed that two d orbitals are involved in macrocyclic π-conjugation. We furthermore demonstrated that Craig-Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables a systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals.

DOI： 10.1021/jacs.3c10250

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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 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

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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）  

DOI： 10.1039/d3qo01661g

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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）  

DOI： 10.1021/acs.jpclett.3c02260

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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

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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

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

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

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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

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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

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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

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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

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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

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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

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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）  

DOI： 10.1039/d2ob01410f

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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）  

DOI： 10.1002/ejoc.202200770

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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

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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

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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）  

DOI： 10.1039/d2cp00295g

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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

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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

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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）  

DOI： 10.1246/bcsj.20220026

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  

DOI： 10.1246/cl.210754

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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  

DOI： 10.1246/cl.210777

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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）  

DOI： 10.1002/anie.202112456

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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  

<p>A radical anion of Ni(II) <i>meso</i>-dimesitylnorcorrole was prepared and isolated upon chemical reduction of the corresponding neutral species with cobaltocene (Co^IICp₂). 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.</p>

DOI： 10.1246/cl.210715

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  

DOI： 10.1002/anie.202114230

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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）  

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： doi.org/10.1002/chem.202103647

CiNii Research

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1142/S1088424621500887

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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

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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

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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

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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

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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

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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

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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

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

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

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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  

<p>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.</p>

DOI： 10.1246/cl.210074

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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

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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

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.202005077

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.orglett.1c00253

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）  

DOI： 10.1002/ajoc.202000722

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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）  

DOI： 10.1002/anie.202013542

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d0cc07804b

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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

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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）  

DOI： 10.1039/d0cc06495e

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.202001129

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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）  

DOI： 10.1039/d0dt02727h

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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）  

DOI： 10.1039/d0dt03143g

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.0c02166

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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）  

DOI： 10.1038/s41467-020-17684-6

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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）  

DOI： 10.1021/jacs.0c04096

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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）  

DOI： 10.1002/chem.202002053

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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）  

DOI： 10.1039/d0cc02543g

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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  

<p>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。</p>

DOI： 10.20665/kakyoshi.68.6_268

CiNii Research

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）  

DOI： 10.1021/acs.orglett.0c01402

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.200083

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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）  

DOI： 10.1142/S108842461950069X

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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）  

DOI： 10.1002/chem.201905402

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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.

CiNii Research

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.9b01655

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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）  

DOI： 10.1021/jacs.9b09556

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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）  

DOI： 10.1021/acs.orglett.9b03699

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - A European Journal  

DOI： 10.1002/chem.201903639

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.190369

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DOI： 10.1021/acs.organomet.9b00303

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201902123

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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）  

DOI： 10.1038/s41467-019-11467-4

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.3390/molecules24132433

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DOI： 10.1002/chem.201901292

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DOI： 10.1021/acs.orglett.9b01066

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DOI： 10.1002/cplu.201900068

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DOI： 10.1021/jacs.8b13169

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c8cc07489e

研究データ保存先URL： http://orcid.org/0000-0002-5321-2205

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cphc.201800745

研究データ保存先URL： http://orcid.org/0000-0002-5321-2205

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.8b04673

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.8b02327

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c8cc01937a

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.8b00798

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記述言語：英語  

DOI： 10.1039/c7qm00593h

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201712961

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7sc04453d

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.orglett.7b03764

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.jinorgbio.2017.10.012

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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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 有機合成化学協会  

DOI： 10.5059/YUKIGOSEIKYOKAISHI.76.37

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201707212

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.joc.7b01899

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201706134

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.orglett.7b02390

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.organomet.7b00611

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7dt01838j

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.201700840

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7qm00176b

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7cc04776b

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/ncomms15984

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.170363

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7tc01270e

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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.

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201701474

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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.

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201700729

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.orglett.7b01074

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c6qo00629a

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.chemrev.6b00427

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c6ob02775j

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c6cc09444a

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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

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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

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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

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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

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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

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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

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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

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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 応用物理学会  

DOI： 10.11470/jsapmeeting.2016.1.0_3881

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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

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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

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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

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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.

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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 Zn^II-Cu^I-Zn^II heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a [46]decaphyrin with Zn^II ions to produce a 46π decaphyrin bis(Zn^II) complex and its subsequent metalation with Cu^II ion. In the second metalation step, it has been shown that Cu^II ion is reduced to a Cu^I ion in the complex and a dianionic bis(Zn^II) 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: Cu^II metalation of a [46]decaphyrin bis(Zn^II) complex gave a Zn^II-Cu^I-Zn^II heterotrimetal complex of decaphyrin consisting of a central Cu^I ion and a monoanionic 45π radical of decaphyrin.

DOI： 10.1002/anie.201505130

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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.

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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 <i>meso</i>-acetylporphyrin because of the coplanar orientation of the carbonyl groups to the porphyrin &pi; system.

DOI： 10.1246/cl.140470

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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 &pi;-extended fluorubins from perylene bisimides. Iridium-catalyzed direct borylation, the Suzuki&ndash;Miyaura cross-coupling, and an acid-condensation sequence afforded &pi;-extended fluorubins <b>1</b> in moderate yields. X-ray diffraction analysis revealed a planar structure of <b>1</b>. In addition, optical analysis and DFT calculations indicated the presence of intramolecular charge-transfer interactions in <b>1c</b>.

DOI： 10.1246/cl.140330

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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

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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

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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

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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

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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  

The treatment of an antiaromatic norcorrole NiII 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 NiII 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. This looks like a good spot for Si: The treatment of an antiaromatic norcorrole NiII complex with a kinetically stabilized silylene provided ring-expansion products in excellent yields by highly regioselective insertion into the β-β pyrrolic C-C bonds. The absorption spectrum of the resulting silicon-containing NiII porphyrinoid is substantially red-shifted into the near-infrared region. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/anie.201309921

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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

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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：東京 : 有機合成化学協会  

CiNii Research

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

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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

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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

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201306905

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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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  

DOI： 10.1246/cl.2011.902

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/om100644n

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja104842h

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja101040s

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.200906017

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp905675x

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ol902294r

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200902143

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：日本語  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja900220y

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/b905859a

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200802541

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200900454

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/asia.200900053

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.apsusc.2009.01.026

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.200805674

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ic8019149

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1055/s-0028-1083267

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/b817941g

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/b819284g

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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

CiNii Research

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja807659h

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja8066385

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja801983d

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp804258q

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.tetlet.2008.01.069

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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.

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ol7028299

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.200701943

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記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.200704407

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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

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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）  

CiNii Research

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<I>meso</I>-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

CiNii Research

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）