Faculty Profiles - SHINOKUBO, Hiroshi

Wittig reaction of cyclobisbiphenylenecarbonyl Reviewed International journal Open Access

Moribe T., Hirano J., Takano H., Shinokubo H., Fukui N.

Beilstein Journal of Organic Chemistry Vol. 21 page： 1454 - 1461 2025.7

Language：English Publishing type：Research paper (scientific journal) Publisher：Beilstein Journal of Organic Chemistry

Cyclobisbiphenylenecarbonyl (CBBC) represents a readily available chiral figure-eight macrocycle containing two carbonyl groups. However, the transformation of the carbonyl groups has been unexplored. Herein, we conducted the Wittig reaction of CBBC with methylenetriphenylphosphorane to furnish two chiral macrocycles containing one or two exocyclic olefin units. Owing to the transformation of carbonyl groups, the resulting products exhibit several unique physical and chemical properties: (1) the enhancement of configurational stability, (2) the appearance of fluorescence, and (3) the reductive carbon–carbon-bond formation between carbonyl and alkene units.

DOI： 10.3762/bjoc.21.107

Open Access

Highly Electron‐Donating Antiaromatic N,N′‐Dimethyldiazaporphyrins via Reductive Dimethylation Invited Reviewed International journal Open Access

Kohei Ohtake, Hideaki Takano, Hiroshi Shinokubo

ChemistryEurope Vol. 3 page： e20250010 2025.6

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley

Ni(II) N,N′‐dimethyl‐5,15‐diazaporhyrins are efficiently prepared through reductive dimethylation of 5,15‐diazaporphyrin Ni(II) complexes with sodium dispersion in the presence of dimethyl sulfate. The obtained reduced diazaporphyrins exhibit highly upfield‐shifted 1H NMR spectra and narrowed HOMO–LUMO gaps originating from their distinct antiaromatic nature. The electrochemical analysis reveals their highly electron‐donating property, which leads to the formation of a charge transfer (CT) complex with tetracyanoquinodimethane (TCNQ) as an electron acceptor. The CT complex of Ni(II) N,N′‐dimethyl‐10,20‐diphenyl‐5,15‐diazaporphyrin with TCNQ exhibits alternate π‐stacking orientation in the solid state. N,N′‐Dimethyl‐5,15‐diazaporphyrins also interact with C60 in the solid state to yield cocrystals.

DOI： 10.1002/ceur.202500109

Open Access

Chiral Aromatic Micelles as Chiroptical Host Tools for Large Metallodyes in Water Reviewed International journal Open Access

Yoshihisa Hashimoto, Yuya Tanaka, Si-Yu Liu, Hiroshi Shinokubo, Michito Yoshizawa

Journal of the American Chemical Society Vol. 147 ( 26 ) page： 23060 - 23067 2025.6

Oxidation of Platina(II)corrole to Platina(IV)corrole Reviewed International journal Open Access

Satoshi Kato, Kazuki Miwa, Hideaki Takano, Hiroshi Shinokubo

Inorganic Chemistry Vol. 64 ( 22 ) page： 10916 - 10922 2025.5

Development of Stable π -Conjugated Hydrocarbons with Narrow HOMO-LUMO Gaps Invited Reviewed International journal

Fukui N., Shinokubo H.

Yuki Gosei Kagaku Kyokaishi Journal of Synthetic Organic Chemistry Vol. 83 ( 5 ) page： 455 - 463 2025.5

Authorship：Last author,　Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Yuki Gosei Kagaku Kyokaishi Journal of Synthetic Organic Chemistry

Carbon and hydrogen are fundamental components of organic molecules. Various functional π - systems have been created via the structural modification of conventional π -conjugated hydrocarbons. Novel π -conjugated hydrocarbon skeletons with attractive electronic structures are a source of novel functional materials. Notably, π -conjugated hydrocarbons with a narrow HOMO-LUMO gap are attractive research targets. Hydrocarbons with antiaromaticity or diradical character often exhibit narrow HOMO-LUMO gaps. However, these molecules are inherently reactive, thus requiring kinetic stabilization by sterically hindered peripheral substituents. This article describes the synthesis and properties of as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, indeno[1,2,3,4-pqra]perylene, and its π - extended derivatives. These π -conjugated hydrocarbons are sufficiently stable under ambient conditions despite their narrow HOMO-LUMO gaps.

DOI： 10.5059/yukigoseikyokaishi.83.455

Rolling two-dimensional covalent organic framework (COF) sheets into one-dimensional electronic and proton-conductive nanotubes Reviewed International coauthorship International journal Open Access

Zhuowei Li, Rajendra Prasad Paitandi, Yusuke Tsutsui, Wakana Matsuda, Masaki Nobuoka, Bin Chen, Samrat Ghosh, Takayuki Tanaka, Masayuki Suda, Tong Zhu, Hiroshi Kageyama, Yoshihiro Miyake, Hiroshi Shinokubo, Makito Takagi, Tomomi Shimazaki, Masanori Tachikawa, Katsuaki Suzuki, Hironori Kaji, Yasunobu Ando, Takahiro Ezaki, Shu Seki

Proceedings of the National Academy of Sciences Vol. 122 ( 16 ) page： e2424314122 2025.4

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Proceedings of the National Academy of Sciences

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes (CNTs), herein we report the in situ transformation of 2D π-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile “roll-sheets” self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not for the corresponding pyrene COF, although both possess similar chemical structures. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties were realized, reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited concerted electronic- and proton-conducting nature with stable conducting pathways at ambient conditions. The nitrogen centers act simultaneously as the site for charge carrier doping and proton acceptors, as evidenced by the high photo- and electrical conductivity, as well as the record proton conductivity (σ = 1.98 S cm −1 ) results. The present diazapyrene-based 1D nanotubular COF serves as a unique materials platform with electronic conduction in the wall and proton conduction in the core, respectively.

DOI： 10.1073/pnas.2424314122

Effect of structural bending on the photophysical properties of perylene bisimide Invited Reviewed International journal Open Access

Hikaru Sotome, Masahiro Higashi, Yuki Tanaka, Hiroshi Shinokubo, Yasuhiro Kobori, Norihito Fukui

The Journal of Chemical Physics Vol. 162 ( 11 ) page： 114305 2025.3

Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism Reviewed International coauthorship International journal Open Access

Keita Tajima, Christophe Bucher, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo

JACS Au Vol. 5 ( 3 ) page： 1421 - 1428 2025.3

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)

DOI： 10.1021/jacsau.5c00037

Other Link： https://doi.org/10.1021/jacsau.5c00037

Synthesis and Properties of Donor-Acceptor-Type Cyclobisbiphenylenecarbonyls Reviewed International journal

Nishimoto, E; Ikai, T; Shinokubo, H; Fukui, N

CHEMISTRY-A EUROPEAN JOURNAL Vol. 31 ( 15 ) page： e202404194 2025.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Chemistry - A European Journal

The scalable synthesis of figure-eight π-systems is challenging for the conventional bottom-up approach. We have recently reported that the oxidative inner-bond cleavage of commercially available dibenzo[g,p]chrysene efficiently furnishes a figure-eight π-acceptor, cyclobisbiphenylenecarbonyl (CBBC), in large quantity. Furthermore, its donor–acceptor-type derivative with four N-carbazolyl substituents at the meta-positions of the carbonyl groups exhibited thermally activated delayed fluorescence (TADF) and circularly polarized luminescence (CPL) with a high |gCPL| value of 1.0×10−2. Herein, we synthesized nine donor–acceptor-type CBBC derivatives by changing the donor substituents and their positions. Compared to previously reported carbazole-substituted CBBC, tetramethylcarbazole- and 9,10-dihydro-9,9-dimethylacridine-substituted derivatives exhibited enhanced emission quantum yields and accelerated reverse intersystem crossing. The functionalization of the para-positions of the carbonyl groups resulted in better tunability of emission colors rather than meta-functionalization, whose color variation ranges from light blue to red. The incorporation of bulky substituents at the meta-positions of the carbonyl groups induced the conformational change to a distorted ring structure. Investigation of the substituent effect on the chiroptical properties revealed that the introduction of less bulky donor units such as carbazole at the meta-positions of the carbonyl groups is effective in achieving high |gCPL| values.

DOI： 10.1002/chem.202404194

PubMed

Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202404194

Diradical character view of energy stabilization in π-stacked dimers of antiaromatic molecules Reviewed International journal Open Access

Hiroshi Shinokubo

Chemistry Letters Vol. 53 ( 12 ) page： upae224 2024.12

Catalytic Construction of Stereogenic Boron Center on BODIPY via Enantioselective Suzuki–Miyaura Coupling Reviewed International journal

Aiko Kondo, Hideaki Takano, Hiroshi Shinokubo

Chemistry Letters 2024.11

Bowl-Shaped Anthracene-Fused Antiaromatic Ni(II) Norcorrole: Synthesis, Structure, Assembly with C60, and Photothermal Conversion Reviewed International journal

Kaisheng Wang, Aninda Ghosh, Daiki Shimizu, Hideaki Takano, Masatoshi Ishida, Ryohei Kishi, Hiroshi Shinokubo

Angewandte Chemie International Edition Vol. 64 ( 7 ) page： e202419289 2024.11

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal)

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

DOI： 10.1002/anie.202419289

Other Link： https://onlinelibrary.wiley.com/doi/10.1002/anie.202419289

Zig-zag-fused π-extended BODIPYs via gold-catalysed cycloisomerisation Invited Reviewed International journal

Fumika Ohashi, Hideaki Takano, Hiroshi Shinokubo

Chemical Communications Vol. 60 ( 88 ) page： 12892 - 12895 2024.11

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

An efficient gold-catalysed intramolecular cycloisomerisation of BODIPYs provides seven-membered-ring-fused BODIPYs on the zig-zag edge. The fused π-extended BODIPYs exhibit unique photophysical properties including NIR absorption and emission.

DOI： 10.1039/d4cc04416a

Synthesis and electron-transporting properties of phenazine bisimides Reviewed International journal

Keita Tajima, Taito Moribe, Kyohei Matsuo, Hiroko Yamada, Shu Seki, Seiya Yokokura, Toshihiro Shimada, Norihito Fukui, Hiroshi Shinokubo

Journal of Materials Chemistry C Vol. 13 ( 2 ) page： 655 - 662 2024.10

Synthesis of four regioisomeric Ni(II) azacorroles via oxidative ring-expansion of prefunctionalised norcorroles Reviewed International coauthorship International journal

Sha Li, Shaowei Zhang, Kohei Ohtake, Hiroshi Shinokubo, Xiaofang Li

Organic Chemistry Frontiers Vol. 11 ( 20 ) page： 5928 - 5937 2024.10

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

We explored the synthesis and properties of four regioisomeric Ni(ii) azacorroles. The results revealed that the substituent at different pyrrole positions exerted different effects on the electronic structures.

DOI： 10.1039/d4qo01415d

Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons Reviewed International coauthorship International journal

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

Journal of the American Chemical Society Vol. 146 ( 43 ) page： 29383 - 29390 2024.9

An n-type semiconducting diazaporphyrin-based hydrogen-bonded organic framework Reviewed International journal

Takahiro Sakurai, Tappei Tanabe, Hiroaki Iguchi, Zhuowei Li, Wakana Matsuda, Yusuke Tsutsui, Shu Seki, Ryotaro Matsuda, Hiroshi Shinokubo

Chemical Science Vol. 15 ( 32 ) page： 12922 - 12927 2024.8

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

A Ni(ii) diazaporphyrin with carboxy groups afforded a stable HOF through intermolecular hydrogen-bonding interactions, which exhibited high semiconductivity as well as stability toward heating and various solvents.

DOI： 10.1039/d4sc03455d

Other Link： https://doi.org/10.1039/D4SC03455D

Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators Invited Reviewed International journal Open Access

Siham Asyiqin Shafie, Ryo Nozawa, Hideaki Takano, Hiroshi Shinokubo

Beilstein Journal of Organic Chemistry Vol. 20 page： 1967 - 1972 2024.8

Ultrafine Spatial Modulation of Diazapyrene-Based Two-Dimensional Conjugated Covalent Organic Frameworks Reviewed International coauthorship International journal

Zhuowei Li, Takahiro Tsuneyuki, Rajendra Prasad Paitandi, Takumi Nakazato, Masahiro Odawara, Yusuke Tsutsui, Takayuki Tanaka, Yoshihiro Miyake, Hiroshi Shinokubo, Makito Takagi, Tomomi Shimazaki, Masanori Tachikawa, Katsuaki Suzuki, Hironori Kaji, Samrat Ghosh, Shu Seki

Journal of the American Chemical Society Vol. 146 ( 33 ) page： 23497 - 23507 2024.8

Homochiral and Heterochiral Self‐Sorting Assemblies of Antiaromatic Ni(II) Norcorrole Dimers Reviewed International journal

Si‐Yu Liu, Sha Li, Shusaku Ukai, Ryo Nozawa, Norihito Fukui, Ryota Sugimori, Ryohei Kishi, Hiroshi Shinokubo

Chemistry – A European Journal Vol. 30 ( 39 ) page： e202400292 2024.7

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley

Abstract

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

DOI： 10.1002/chem.202400292

Synthesis of sterically congested double helicene by alkyne cycloisomerization Invited Reviewed International journal

Junichiro Hirano, Sayaka Miyoshi, Eiji Yashima, Tomoyuki Ikai, Hiroshi Shinokubo, Norihito Fukui

Chemical Communications Vol. 60 ( 47 ) page： 6035 - 6038 2024.6

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

Alkyne cycloisomerization of 2,7,10,15-tetra(ortho-alkynylphenyl)benzo[g,p]chrysene containing bulky 4-alkoxy-2,6-dimethylphenyl groups at the alkyne terminals selectively proceeded at the sterically crowded bay-region.

DOI： 10.1039/d4cc01573h

End-to-End Bent Perylene Bisimide Cyclophanes by Double Sulfur Extrusion Reviewed International journal

Yuki Tanaka, Keita Tajima, Ryota Kusumoto, Yasuhiro Kobori, Norihito Fukui, Hiroshi Shinokubo

Journal of the American Chemical Society Vol. 146 ( 23 ) page： 16332 - 16339 2024.5

Norcorroles as antiaromatic π-electronic systems that form dimension-controlled assemblies Reviewed International journal

Soh Ishikawa, Kazuhisa Yamasumi, Shinya Sugiura, Shunsuke Sato, Go Watanabe, Yun Hee Koo, Shu Seki, Yuya Bando, Yohei Haketa, Hiroshi Shinokubo, Hiromitsu Maeda

Chemical Science Vol. 15 ( 20 ) page： 7603 - 7609 2024.5

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

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

DOI： 10.1039/d4sc01633e

Changing aromatic properties through stacking: the face-to-face dimer of Ni(II) bis(pentafluorophenyl)norcorrole Reviewed International coauthorship International journal

Qian Wang, Dage Sundholm, Jürgen Gauss, Tommaso Nottoli, Filippo Lipparini, Shota Kino, Shusaku Ukai, Norihito Fukui, Hiroshi Shinokubo

Physical Chemistry Chemical Physics Vol. 26 ( 20 ) page： 14777 - 14786 2024.5

Authorship：Last author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

The diatropic (red) and paratropic (yellow) current density of the antiaromatic Ni(ii) bis(pentafluorophenyl)norcorrole and of its aromatic face-to-face stacked dimer.

DOI： 10.1039/d4cp00968a

Inner-bond-cleavage approach to figure-eight macrocycles from planar aromatic hydrocarbons Reviewed International journal

Journal of the American Chemical Society Vol. 146 page： 29383 - 29390 2024.5

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)

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

DOI： 10.26434/chemrxiv-2024-j1xxr

Triply-Linked Porphyrin−Norcorrole Hybrid with Singlet Diradical Character Reviewed International coauthorship International journal

Kaisheng Wang, Satoru Ito, Shuang Ren, Daiki Shimizu, Norihito Fukui, Ryohei Kishi, Qiang Liu, Atsuhiro Osuka, Jianxin Song, Hiroshi Shinokubo

Angewandte Chemie International Edition Vol. 63 ( 16 ) page： e202401233 2024.4

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)

Norcorrole Ni(II) complexes have recently received considerable attention as readily accessible antiaromatic molecules. Their high stabil-ity under ambient conditions and easy synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of directly meso−meso singly-linked porphyrin−norcorrole hybrids and triply-linked porphy-rin−norcorrole hybrids. The singly-linked and triply-linked porphyrin−norcorrole hybrids were fully characterized, including their X-ray structural analysis. Because of their orthogonal conformation, singly-linked hybrids maintained the individual electronic property of por-phyrin and norcorrole subunits The triply-linked hybrid showed a significant decrease in the HOMO–LUMO gaps, the paratropic ring current in the norcorrole subunit, and the diamagnetic ring current in the porphyrin subunit. Furthermore, the triply-linked hybrid exhib-ited singlet diradical characteristics, confirmed by VT-NMR, ESR, and SQUID experiments.

DOI： 10.1002/anie.202401233

Close Stacking of Antiaromatic Ni(II) Norcorrole Originating from a Four-Electron Multicentered Bonding Interaction Reviewed International coauthorship International journal

Shota Kino, Shusaku Ukai, Norihito Fukui, Rie Haruki, Reiji Kumai, Qian Wang, Satoshi Horike, Quan Manh Phung, Dage Sundholm, Hiroshi Shinokubo

Journal of the American Chemical Society Vol. 146 ( 13 ) page： 9311 - 9317 2024.3

Interaction strength in molecular junctions consisting of π-stacked antiaromatic molecules Reviewed International journal

Shintaro Fujii, Ryoya Tomida, Aoshi Yamane, Kazuki Nabeyama, Harunari Ohkura, Hiroshi Shinokubo, Tomoaki Nishino

Journal of Materials Chemistry C Vol. 12 ( 5 ) page： 1640 - 1643 2024.2

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

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

DOI： 10.1039/d3tc04166b

Excimer Formation Driven by Excited-State Structural Relaxation in a Covalent Aminonaphthalimide Dimer Reviewed International coauthorship International journal

Rui Jing, Yang Li, Keita Tajima, Yan Wan, Norihito Fukui, Hiroshi Shinokubo, Zhuoran Kuang, Andong Xia

The Journal of Physical Chemistry Letters Vol. 15 ( 5 ) page： 1469 - 1476 2024.1

Synthesis and properties of bay-functionalized 9,9′-bifluorenylidene derivatives Reviewed International journal

Junichiro Hirano, Hiroshi Shinokubo, Norihito Fukui

Chemistry Letters Vol. 53 ( 1 ) page： upad015 2024.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Oxford University Press (OUP)

Abstract

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

Other Link： https://academic.oup.com/chemlett/article-pdf/53/1/upad015/56961460/upad015.pdf

Syntheses of Thiophene–Thiophene-Linked Corrorin Dimers with Tunable Near-Infrared Absorption and Distinctive Reactivity Reviewed International coauthorship International journal

Yue Xu, Bin Zhu, Lingfang Zhang, Glib Baryshnikov, Feng Sha, Emiko Nishimoto, Hideaki Takano, Chengjie Li, Xinyan Wu, Hans Ågren, Hiroshi Shinokubo, Yongshu Xie, Qizhao Li

Organic Letters Vol. 26 ( 2 ) page： 571 - 576 2024.1

Metallaantiaromaticity of 10-Platinacorrole Complexes Reviewed International coauthorship International journal

Kazuki Miwa, Tomoya Yokota, Qian Wang, Takahiro Sakurai, Heike Fliegl, Dage Sundholm, Hiroshi Shinokubo

Journal of the American Chemical Society Vol. 146 ( 2 ) page： 1396 - 1402 2024.1

Effect of Internal Substituents on the Properties of Dibenzo[g,p]chrysene Reviewed International journal

Yoshihiro Takeo, Junichiro Hirano, Norihito Fukui, Hiroshi Shinokubo

Organic Letters Vol. 25 ( 47 ) page： 8484 - 8488 2023.11

Effect of internal oxygen substituents on the properties of bowl-shaped aromatic hydrocarbons Reviewed International journal

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

ORGANIC CHEMISTRY FRONTIERS Vol. 10 page： 5895 - 5901 2023.10

Intrinsic Photostability in Dithiolonaphthalimide Achieved by Disulfide Bond-Induced Excited-State Quenching Reviewed International coauthorship International journal

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

The Journal of Physical Chemistry Letters Vol. 14 ( 38 ) page： 8485 - 8492 2023.9

Unique solvent effect of water in radical cyclization reaction Reviewed International journal

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

Chemical Physics Letters Vol. 826 page： 140641 2023.9

Easily Switchable 18π‐, 19π‐, and 20π‐Conjugation of Diazaporphyrin Double‐Pincer Bispalladium Complexes Reviewed International journal

Takahiro Sakurai, Yuya Hiraoka, Hisaaki Tanaka, Yoshihiro Miyake, Norihito Fukui, Hiroshi Shinokubo

Angewandte Chemie International Edition Vol. 62 ( 12 ) page： e202300437 2023.2

Near‐Infrared‐Responsive Hydrocarbons Designed by π‐Extension of Indeno[1,2,3,4‐pgra]perylene at the 1,2,12‐Positions Reviewed International coauthorship International journal

Masaki Kato, Jinseok Kim, Juwon Oh, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo

Chemistry – A European Journal 2023.1

Dinaphthooxepine Bisimide Undergoes Oxygen Extrusion Reaction upon Electron Injection at Room Temperature Reviewed International journal

Mai Odajima, Norihito Fukui, Hiroshi Shinokubo

Organic Letters Vol. 25 ( 1 ) page： 282 - 287 2023.1

One-dimensional stacking array of 10,20-diphenyl-5,15-diazaporphyrin metal complexes Invited Reviewed International journal

Shiho Mori, Takahiro Sakurai, Tsubasa Nishimura, Norihito Fukui, Yoshihiro Miyake, Hiroshi Shinokubo

Journal of Porphyrins and Phthalocyanines Vol. 27 page： 1035 - 1041 2023.1

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：World Scientific Pub Co Pte Ltd

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 [Formula: see text]-stacking array in the solid state. The four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent dominate the crystal packing arrangement. The present study revealed that the meso-nitrogen atom of diazaporphyrins would be used as an inherent hydrogen bonding acceptor to construct supramolecular assemblies.

DOI： 10.1142/s1088424622500997

Diazazethrene bisimide: a strongly electron-accepting π-system synthesized via the incorporation of both imide substituents and imine-type nitrogen atoms into zethrene Reviewed International journal

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

Chemical Science Vol. 14 ( 3 ) page： 635 - 642 2022.12

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

The development of highly electron-accepting π-systems is a fundamentally challenging issue despite their potential applications as various functional materials.

DOI： 10.1039/d2sc05992d

Highly soluble Ni(II) dithienylnorcorrole Invited Reviewed International coauthorship International journal

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

Journal of Porphyrins and Phthalocyanines page： A - E 2022.11

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：World Scientific Pub Co Pte Ltd

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

DOI： 10.1142/S1088424622500730

Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule Reviewed International coauthorship International journal

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

Journal of the American Chemical Society Vol. 145 ( 4 ) page： 2135 - 2141 2022.10

Planarization of a bowl-shaped molecule by triple-decker stacking Reviewed International journal

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

Cell Reports Physical Science Vol. 3 ( 9 ) page： 101045 - 101045 2022.9

d-Mannose-appended 5,15-diazaporphyrin for photodynamic therapy Reviewed International coauthorship International journal

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

ORGANIC & BIOMOLECULAR CHEMISTRY 2022.8

Gram-Scale Diversity-Oriented Synthesis of Dinaphthothiepine Bisimides as Soluble Precursors for Perylene Bisimides Reviewed International journal

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

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol. 2022 ( 31 ) 2022.8

Stepwise N-Methylation of Ruthenium and Cobalt 5,15-Diazaporphyrins: Post-Functionalization of Porphyrinoid Catalysts Reviewed International journal

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

CHEMISTRY-AN ASIAN JOURNAL Vol. 17 ( 14 ) page： e202200305 2022.7

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Chemistry - An Asian Journal

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

DOI： 10.1002/asia.202200305

Protonation‐Induced Antiaromaticity in Octaaza[8]circulenes: Cyclooctatetraene Scaffolds Constrained with Four Amidine Moieties Reviewed International coauthorship International journal

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

Chemistry – An Asian Journal Vol. 17 ( 12 ) page： e202200244 2022.6

Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer Reviewed International coauthorship International journal

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

PHYSICAL CHEMISTRY CHEMICAL PHYSICS Vol. 24 ( 22 ) page： 14007 - 14015 2022.6

Synthesis and Tautomerization of 5-Azaporphyrinium Cations Reviewed International journal

Takiguchi Asahi, Shinokubo Hiroshi

Chemistry Letters Vol. 51 ( 6 ) page： 590 - 593 2022.6

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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 β-ethyl substituents results in the deformation of the inner-cavity to a rectangle. The rectangular cavity and cationic charge induced the unique tautomerization of the inner-NH protons.

DOI： 10.1246/cl.220122

5-Thiaporphyrinium cation: effect of sulphur incorporation on excited state dynamics Reviewed International coauthorship International journal

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

Chemical Communications Vol. 58 ( 40 ) page： 5956 - 5959 2022.5

Diverse Crystal Structures of Ion Pairs Consisting of Oxaporphyrinium Cations and Pentacyanocyclopentadienide Reviewed

Asahi Takiguchi, Hiroki Tanaka, Hiromitsu Maeda, Hiroshi Shinokubo

Bulletin of the Chemical Society of Japan Vol. 95 ( 5 ) page： 796 - 801 2022.3

Synthesis of Dibenzo[h,t]rubicene through Its Internally Dimethoxy-substituted Precursor Reviewed International journal

Kato, Masaki, Fukui, Norihito, Shinokubo, Hiroshi

Chemistry Letters Vol. 51 ( 3 ) page： 288 - 291 2022.3

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

Dibenzo[h,t]rubicene was synthesized from 1,5-dichloroanthraquinone via an internally dimethoxylated intermediate. In contrast to the planar conformation of rubicene, dibenzo[h,t]rubicene adopted a double-helicene-like structure due to the intramolecular steric repulsion around the fused benzene-rings. Theoretical calculation suggests that the helical inversion occurs frequently with an inversion barrier of 4.8 kcal mol−1. The HOMO–LUMO gap of dibenzo[h,t]rubicene is smaller than that of rubicene, resulting in its red-shifted absorption tailing to 690 nm.

DOI： 10.1246/cl.210754

Nitrogen Extrusion of Diazacorrphycenes to Azacorroles and Synthesis of Two Types of Copper 10-Azacorrole Complexes Reviewed International journal

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

Chemistry Letters Vol. 51 ( 3 ) page： 321 - 324 2022.3

Authorship：Last author,　Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

The synthesis of Pd(II) and Cu(II) 10-azacorroles with a meso-NH group has been achieved through the thermal extrusion of one nitrogen atom from the corresponding diazacorrphycene metal complexes. We also found that oxidation of the Cu(II) 10-azacorrole complex afforded another type of copper 10-azacorrole with an imine moiety. The structural, magnetic, and electrochemical properties of these compounds were investigated to disclose the nature of two types of copper 10-azacorroles.

DOI： 10.1246/cl.210777

A Heme-Acquisition Protein Reconstructed with a Cobalt 5-Oxaporphyrinium Cation and Its Growth-Inhibition Activity Toward Multidrug-Resistant Pseudomonas aeruginosa Reviewed International journal

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 61 ( 7 ) page： e202112456 2022.2

Isolation and Structure Analysis of a Ni(II) Norcorrole Radical Anion Reviewed International journal

Ukai Shusaku, Fukui Norihito, Ikeue Takahisa, Shinokubo Hiroshi

Chemistry Letters Vol. 51 ( 2 ) page： 182 - 184 2022.2

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.210715

A Supramolecular Polymer Constituted of Antiaromatic Ni(II) Norcorroles Reviewed International journal

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

Angewandte Chemie International Edition Vol. 61 page： e202114230 2022.2

Indeno[1,2,3,4‐pqra ]Perylene: A Medium‐Sized Aromatic Hydrocarbon Exhibiting Full‐Range Visible‐Light Absorption Reviewed International journal

Masaki Kato, Norihito Fukui, Hiroshi Shinokubo

Chemistry – A European Journal Vol. 28 ( 2 ) page： e202103647 2022.1

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley

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

DOI： 10.1002/chem.202103647

Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202103647

Dual-Ion NiNc Battery: A Sustainable Revolution for Sodium Organic Batteries Reviewed International journal

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

Batteries & Supercaps Vol. 4 ( 10 ) page： 1605 - 1610 2021.10

Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C–H fluorination Reviewed International journal

Shiho Mori, Tsubasa Nishimura, Hiroshi Shinokubo, Yoshihiro Miyake

Journal of Porphyrins and Phthalocyanines Vol. 25 ( 10N12 ) page： 991 - 996 2021.10

Language：English Publishing type：Research paper (scientific journal) Publisher：World Scientific Pub Co Pte Lt

<jats:p> Fluorination of sp<jats:sup>3</jats:sup> C–H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp<jats:sup>3</jats:sup> C–H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp<jats:sup>2</jats:sup>-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp<jats:sup>3</jats:sup> C–H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We also demonstrate the catalysis of chloromanganese(III) 5,15-diazaporphyrins for benzylic fluorination. </jats:p>

DOI： 10.1142/S1088424621500887

Antiaromatic 1,5‐Diaza‐ s ‐indacenes Reviewed International coauthorship International journal

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

Angewandte Chemie International Edition Vol. 60 ( 38 ) page： 20765 - 20770 2021.9

Synthesis of Tetrasilatetrathia[8]circulenes through C-I and C-H Silylation Invited Reviewed International journal

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

Vol. 53 ( 17 ) page： 2995 - 3000 2021.9

Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes Reviewed International coauthorship International journal

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

Journal of the American Chemical Society Vol. 143 ( 28 ) page： 10676 - 10685 2021.7

Non‐Planar Perylene Bisimide Analogues with Inserted Carbonyl and Methylene Subunits Reviewed International journal

Mai Odajima, Keita Tajima, Norihito Fukui, Hiroshi Shinokubo

Angewandte Chemie International Edition Vol. 60 ( 29 ) page： 15838 - 15843 2021.7

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley

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 sigma-dimer. The formation of this C-C bond is dynamically redox-active, i.e., electron injection into the sigma-dimer almost quantitatively regenerated the deprotonated DNCHepBI.

DOI： 10.1002/anie.202104882

Acridino[2,1,9,8‐ klmna ]acridine Bisimides: An Electron‐Deficient π‐System for Robust Radical Anions and n‐Type Organic Semiconductors Reviewed International journal

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

Angewandte Chemie International Edition Vol. 60 ( 25 ) page： 14060 - 14067 2021.6

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：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 cm(2) 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 cm(2) 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 pi-systems.

DOI： 10.1002/anie.202102708

Synthesis and Characterization of 16 pi Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen Reviewed International journal

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

Angewandte Chemie International Edition Vol. 60 ( 25 ) page： 13877 - 13881 2021.6

Quadruply BN‐Fused Tetrathia[8]circulenes with Flexible Frameworks: Synthesis, Structures and Properties Reviewed International journal

Shuhei Akahori, Takahiro Sasamori, Hiroshi Shinokubo, Yoshihiro Miyake

Chemistry – A European Journal Vol. 27 ( 31 ) page： 8178 - 8184 2021.6

Iron hexamesityl-5,15-diazaporphyrin: synthesis, structure and catalytic use for direct oxidation of sp(3) C-H bonds Reviewed International journal

Vol. 50 ( 18 ) page： 6343 - 6348 2021.5

Cationic Nickel(II) Pyridinophane Complexes: Synthesis, Structures and Catalytic Activities for C–H Oxidation Reviewed International journal

Nishimura Tsubasa, Ando Yuki, Shinokubo Hiroshi, Miyake Yoshihiro

Chemistry Letters Vol. 50 ( 5 ) page： 1049 - 1052 2021.5

Language：English Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.210074

Redox-induced reversible [2 + 2] cycloaddition of an etheno-fused diporphyrin Reviewed International journal

Kazuya Miyagawa, Ichiro Hisaki, Norihito Fukui, Hiroshi Shinokubo

Chemical Science Vol. 12 ( 14 ) page： 5224 - 5229 2021.4

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry ({RSC})

3,5-Ethenoporphyrin is a pi -extended porphyrin containing a fused ethene unit between the meso- and beta -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 by H-1 NMR spectroscopy and X-ray diffraction analysis. Importantly, the simultaneous double C-C bond cleavage in the cyclopropane ring in the tetraporphyrin is exceptional among dynamic redox (dyrex) systems to achieve large structural changes, thus offering new insights for the design of novel redox-active functional organic materials for electrochromic dyes, organic batteries, and organic memories.

DOI： 10.1039/d1sc00438g

Synthesis and Properties of an 18π Aromatic Norcorrole P(V) Complex Reviewed International journal

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

Organic Letters Vol. 23 ( 7 ) page： 2826 - 2830 2021.4

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society ({ACS})

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

DOI： 10.1021/acs.orglett.1c00823

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

Akahori Shuhei, Sasamori Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL Vol. 27 page： 5675 - 5682 2021.3

Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation Reviewed

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

Organic Letters Vol. 23 ( 6 ) page： 2099 - 2103 2021.3

Dinaphtho[1,8-bc:1 ',8 '-fg][1,5]dithiocine Bisimide Invited Reviewed

Tanaka Yuki, Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ASIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 10 ( 3 ) page： 541 - 544 2021.2

Dual Emission of a Free-Base 5-Oxaporphyrinium Cation from its cis- and trans-NH Tautomers Reviewed International coauthorship

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 60 ( 6 ) page： 2915 - 2919 2021.2

Complexation of 2,7-diazapyrene with boron for structural and electronic tuning Reviewed

Nakazato Takumi, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS Vol. 57 ( 3 ) page： 327 - 330 2021.1

Dual-ion charge–discharge behaviors of Na–NiNc and NiNc–NiNc batteries Reviewed International journal

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

Materials Advances Vol. 2 ( 7 ) page： 2263 - 2266 2021

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry ({RSC})

Dual-ion Na–organic batteries were provided with anti-aromatic NiNc, exposing inherent charge–discharge behavior with high discharge capacity, high durability, and high Coulombic efficiency with high-density currents.

DOI： 10.1039/D1MA00007A

Hetero[8]circulenes: synthetic progress and intrinsic properties Invited Reviewed

Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS Vol. 56 ( 100 ) 2020.12

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

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

CHEMISTRY-AN ASIAN JOURNAL Vol. 15 ( 22 ) page： 3873 - 3877 2020.11

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

Longevial Jean-Francois, Miyagawa Kazuya, Shinokubo Hiroshi

DALTON TRANSACTIONS Vol. 49 ( 42 ) page： 14786 - 14789 2020.11

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

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

DALTON TRANSACTIONS Vol. 49 ( 41 ) page： 14383 - 14387 2020.11

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

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

INORGANIC CHEMISTRY Vol. 59 ( 21 ) page： 15751 - 15756 2020.11

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

NATURE COMMUNICATIONS Vol. 11 ( 1 ) 2020.8

Dinaphthothiepine Bisimide and Its Sulfoxide: Soluble Precursors for Perylene Bisimide Reviewed

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 142 ( 27 ) page： 11663 - 11668 2020.7

meso-Diazacorrphycenes: Neighboring Effect of Two Nitrogen Atoms Reviewed

Yagi Atsumi, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL Vol. 26 ( 37 ) page： 8210 - 8213 2020.7

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

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

CHEMICAL COMMUNICATIONS Vol. 56 ( 50 ) page： 6846 - 6849 2020.6

新形式の芳香族化合物の合成を目指して Reviewed International journal

忍久保洋

化学と教育 Vol. 68 ( 6 ) page： 268 - 269 2020.6

Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：公益社団法人日本化学会

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

DOI： 10.20665/kakyoshi.68.6_268

Reactions of Antiaromatic Norcorrole Ni(II) Complex with Carbenes Reviewed

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

ORGANIC LETTERS Vol. 22 ( 11 ) page： 4400 - 4403 2020.6

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

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

CHEMISTRY LETTERS Vol. 49 ( 5 ) page： 465 - 468 2020.5

Synthesis and properties of 5-aza-15-thiaporphyrins Invited Reviewed

Yamashita Daisuke, Omori Hiroto, Fukui Norihito, Shinokubo Hiroshi

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES Vol. 24 ( 1-3 ) page： 84 - 89 2020.3

Site-Selective N-Methylation of 5,15-Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues Reviewed International coauthorship

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 26 ( 12 ) page： 2754 - 2760 2020.2

Site‐Selective N‐Methylation of 5,15‐Diazaporphyrins: Reactive Cationic Porphyrinoids that Provide Isoporphyrin Analogues Reviewed International journal

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

Chemistry–A European Journal Vol. 26 ( 12 ) page： 2754 - 2760 2020.2

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)

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.

5,5,15,15‐Tetraoxo‐5,15‐Dithiaporphyrin as a Highly Electron‐Deficient Porphyrinic Ligand Reviewed

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

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

JOURNAL OF ORGANIC CHEMISTRY Vol. 85 ( 1 ) page： 62 - 69 2020.1

Inserting Nitrogen: An Effective Concept To Create Nonplanar and Stimuli-Responsive Perylene Bisimide Analogues Reviewed International coauthorship

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 141 ( 50 ) page： 19807 - 19816 2019.12

Aggregation-Induced Emission of Nitrogen-Bridged Naphthalene Monoimide Dimers Reviewed

Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS Vol. 21 ( 23 ) page： 9516 - 9520 2019.12

Atsumi Yagi, Takeshi Kondo, Daisuke Yamashita, Naruhiko Wachi, Hiroto Omori, Norihito Fukui, Takahisa Ikeue, Hiroshi Shinokubo

Chemistry – A European Journal Vol. 25 ( 68 ) page： 15580 - 15585 2019.12

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

Ushiyama Ayako, Shinokubo Hiroshi, Hiroto Satoru

CHEMISTRY LETTERS Vol. 48 ( 9 ) page： 1069 - 1072 2019.9

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

Omori Hiroto, Shinokubo Hiroshi

ORGANOMETALLICS Vol. 38 ( 15 ) page： 2878 - 2882 2019.8

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

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 25 ( 45 ) page： 10571 - 10574 2019.8

Three-dimensional aromaticity in an antiaromatic cyclophane Reviewed International coauthorship

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

NATURE COMMUNICATIONS Vol. 10 2019.8

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

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

MOLECULES Vol. 24 ( 13 ) 2019.7

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

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 25 ( 32 ) page： 7618 - 7622 2019.6

Synthesis of Hydroxyisooxophlorins by Oxidative Degradation of meso-Hydroxyporphyrins

Takiguchi Asahi, Fukui Norihito, Shinokubo Hiroshi

ORGANIC LETTERS Vol. 21 ( 11 ) page： 3950 - 3953 2019.6

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

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

CHEMPLUSCHEM Vol. 84 ( 6 ) page： 623 - 626 2019.6

Synthesis of Dihydropyrazine-fused Porphyrin Dimers

Takiguchi Asahi, Wakita Mana, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY LETTERS Vol. 48 ( 4 ) page： 371 - 373 2019.4

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

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 141 ( 12 ) page： 4800 - 4805 2019.3

Diazachlorin and diazabacteriochlorin for one- and two-photon photodynamic therapy. Reviewed

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

Chemical communications (Cambridge, England) Vol. 54 ( 98 ) page： 13829 - 13832 2018.12

Theoretical Study on Open-Shell Singlet Character and Second Hyperpolarizabilities in Cofacial π-Stacked Dimers Composed of Weak Open-Shell Antiaromatic Porphyrins Reviewed

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

ChemPhysChem Vol. 19 ( 21 ) page： 2863 - 2871 2018.11

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

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 140 ( 27 ) page： 8392-8395 2018.7

Azabuckybowl-Based Molecular Tweezers as C-60 and C-70 Receptors Reviewed

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 140 ( 20 ) page： 6336-6342 2018.5

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

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

CHEMICAL COMMUNICATIONS Vol. 54 ( 41 ) page： 5177-5180 2018.5

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

Yokoi Hiroki, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 140 ( 13 ) page： 4649-4655 2018.4

Figuration of bowl-shaped pi-conjugated molecules: properties and functions Invited Reviewed

Saito Masaichi, Shinokubo Hiroshi, Sakurai Hidehiro

MATERIALS CHEMISTRY FRONTIERS Vol. 2 ( 4 ) page： 635 - 661 2018.4

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

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 57 ( 8 ) page： 2209-2213 2018.2

Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C-60 Reviewed

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

CHEMICAL SCIENCE Vol. 9 ( 4 ) page： 819-824 2018.1

Synthesis and Photodynamics of Tetragermatetrathia[8]circulene Reviewed

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

ORGANIC LETTERS Vol. 20 ( 1 ) page： 304-307 2018.1

Nickel (II) pyrrocorphin: Enhanced binding ability in a highly reduced porphyrin complex. Reviewed

Ide Y, Kuwahara T, Takeshita S, Fujishiro R, Suzuki M, Mori S, Shinokubo H, Nakamura M, Yoshino K, Ikeue T

Journal of inorganic biochemistry Vol. 178 page： 115 - 124 2018.1

Synthesis of Heteroatom-Containing Curved pi-Conjugated Molecules Reviewed

Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN Vol. 76 ( 1 ) page： 37-44 2018.1

Synthesis of Heteroatom-Containing Curved pi-Conjugated Molecules Reviewed International journal

Hiroto, Satoru, Shinokubo, Hiroshi

Journal of Synthetic Organic Chemistry Japan Vol. 76 ( 1 ) page： 37 - 44 2018

Authorship：Last author,　Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Society of Synthetic Organic Chemistry, Japan

Recently, π-conjugated molecules with curved-π surface have attracted considerable interest for their unique properties originating from their curved structures. However, most of them consist of only carbon and hydrogen atoms. In these situations, we have developed novel synthetic protocols for construction of distorted structures directly from 2D π-conjugated molecules under mild reaction conditions. By applying phenol and aniline oxidation methods, we have succeeded in the synthesis of highly distorted cyclophanes, π-extended heterohelicenes, and highly twisted porphyrin oligomers. Furthermore, we have succeeded in the synthesis of a nitrogen-embedded buckybowl as a novel bowl-shaped π-conjugated molecule with a pyrrolic nitrogen in its skeleton. These heteroatom containing curved-π conjugated molecules exhibit unique characteristics due to the combination of the curved structure with heteroatoms such as circularly polarized luminescence, strong C60 binding, and near IR electrochromism. We believe that the chemistry of heteroatom containing curved-π conjugated molecules would enhance the potential of three-dimensional π-conjugated molecules for molecular materials.

DOI： 10.5059/YUKIGOSEIKYOKAISHI.76.37

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

Uehara H, Shisaka Y, Nishimura T, Sugimoto H, Shiro Y, Miyake Y, Shinokubo H, Watanabe Y, Shoji O

Angewandte Chemie (International ed. in English) Vol. 56 ( 48 ) page： 15279 - 15283 2017.11

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

Kawashima Hiroyuki, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF ORGANIC CHEMISTRY Vol. 82 ( 19 ) page： 10425 - 10432 2017.10

Shaping Antiaromatic -Systems by Metalation: Synthesis of a Bowl-Shaped Antiaromatic Palladium Norcorrole Reviewed

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 56 ( 39 ) page： 11822 - 11825 2017.9

Synthesis and Properties of meso-Arylated Corrphycenes. Reviewed

Nozawa R, Shinokubo H

Organic letters Vol. 19 ( 18 ) page： 4928 - 4931 2017.9

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

Kamatsuka Takuto, Shinokubo Hiroshi, Miyake Yoshihiro

ORGANOMETALLICS Vol. 36 ( 17 ) page： 3429 - 3434 2017.9

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

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

DALTON TRANSACTIONS Vol. 46 ( 33 ) page： 10802 - 10808 2017.9

pi-Extended Dihydrophenazines with Three-State NIR Electrochromism Involving Large Conformational Changes Reviewed

Nagasaki Juri, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-AN ASIAN JOURNAL Vol. 12 ( 17 ) page： 2311 - 2317 2017.9

Direct amination of the antiaromatic Ni-II norcorrole Reviewed

Yoshida Takuya, Shinokubo Hiroshi

MATERIALS CHEMISTRY FRONTIERS Vol. 1 ( 9 ) page： 1853 - 1857 2017.9

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

Ando Yuki, Kamatsuka Takuto, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS Vol. 53 ( 65 ) page： 9136-9138 2017.8

Highly-conducting molecular circuits based on antiaromaticity Reviewed

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

NATURE COMMUNICATIONS Vol. 8 2017.7

Synthesis, Properties, and Reactivities of Ruthenium(II) Carbonyl 5,15-Diazaporphyrins Reviewed

Nishimura Tsubasa, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMISTRY LETTERS Vol. 46 ( 7 ) page： 995 - 997 2017.7

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

Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

JOURNAL OF MATERIALS CHEMISTRY C Vol. 5 ( 22 ) page： 5310 - 5315 2017.6

NIR mechanochromic behaviours of a tetracyanoethylene-bridged hexa-peri-hexabenzocoronene dimer and trimer through dissociation of C–C bonds Reviewed International journal

Oda Kazuma, Hiroto Satoru, Shinokubo Hiroshi

Journal of Materials Chemistry C Vol. 5 ( 22 ) page： 5310 - 5315 2017.6

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)

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

10-Silacorroles Exhibiting Near-Infrared Absorption and Emission

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL Vol. 23 ( 33 ) page： 7866-7870 2017.6

10-Silacorroles Exhibiting NIR Absorption and Emission Reviewed International journal

Omori Hiroto, Hiroto Satoru, Shinokubo Hiroshi

CHEMISTRY-A EUROPEAN JOURNAL Vol. 22 ( 33 ) page： 7866 - 7870 2017.6

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)

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.

DOI： 10.1002/chem.201783363

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

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 23 ( 29 ) page： 6948 - 6952 2017.5

Synthesis of Tetraaza[8]circulenes from Tetrathia[8]circulenes through an SNAr-Based Process Reviewed

Nagata Yuya, Kato Shohei, Miyake Yoshihiro, Shinokubo Hiroshi

ORGANIC LETTERS Vol. 19 ( 10 ) page： 2718 - 2721 2017.5

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

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

ORGANIC CHEMISTRY FRONTIERS Vol. 4 ( 5 ) page： 664-667 2017.5

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies Invited Reviewed

Hiroto Satoru, Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL REVIEWS Vol. 117 ( 4 ) page： 2910 - 3043 2017.2

Synthesis of bright red-emissive dicyanoetheno-bridged hexa-peri-hexabenzocoronene dimers Reviewed

Oda Kazuma, Hiroto Satoru, Hisaki Ichiro, Shinokubo Hiroshi

ORGANIC & BIOMOLECULAR CHEMISTRY Vol. 15 ( 6 ) page： 1426 - 1434 2017.2

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

Yoshida Takuya, Sakamaki Daisuke, Seki Shu, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS Vol. 53 ( 6 ) page： 1112 - 1115 2017.1

Stacked antiaromatic porphyrins Reviewed International journal

Nozawa, R., Tanaka, H., Cha, W.-Y., Hong, Y., Hisaki, I., Shimizu, S., Shin, J.-Y., Kowalczyk, T., Irle, S., Kim, D., Shinokubo, H.

Nature Communications Vol. 7 page： 13620 2016.11

Reversible Carbon–Carbon Bond Breaking and Spin Equilibria in Bis(pyrimidinenorcorrole) Reviewed International journal

Liu, B., Yoshida, T., Li, X., Stępień, M., Shinokubo, H., Chmielewski, P.J.

Angewandte Chemie - International Edition Vol. 55 ( 42 ) page： 13142 - 13146 2016.10

Syntheses and Properties of Antiaromatic Porphyrinoids Reviewed International journal

Satoru Hiroto, Hiroshi Shinokubo

Handbook of Porphyrin Science (Volumes 36 – 40) 2016.7

β-to-β 2,5-Pyrrolylene-Linked Cyclic Porphyrin Oligomers Reviewed International journal

Rao, Y., Kim, J.O., Kim, W., Zhong, G., Yin, B., Zhou, M., Shinokubo, H., Aratani, N., Tanaka, T., Liu, S., Osuka, A., Kim, D., Song, J.

Chemistry - A European Journal Vol. 22 ( 26 ) page： 8801 - 8804 2016.6

Synthesis of Free-Base 10-Azacorroles Reviewed International journal

Omori, H., Hiroto, S., Shinokubo, H.

Organic Letters Vol. 18 ( 12 ) page： 2978 - 2981 2016.6

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal)

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

DOI： 10.1021/acs.orglett.6b01323

Fully-substituted 1,3-butadienes as π-conjugated linkers between pyrenes Reviewed International journal

Oda, K., Hiroto, S., Sakamaki, D., Seki, S., Shinokubo, H.

Chemistry Letters Vol. 45 ( 4 ) page： 403 - 405 2016.4

Authorship：Last author,　Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.151181

Control of Conformation and Chirality of Nonplanar π-Conjugated Diporphyrins Using Substituents and Axial Ligands Reviewed International journal

Ito, S., Hiroto, S., Ousaka, N., Yashima, E., Shinokubo, H.

Chemistry - An Asian Journal Vol. 11 ( 6 ) page： 936 - 942 2016.3

Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids Reviewed International journal

Yamaji, A., Tsurugi, H., Miyake, Y., Mashima, K., Shinokubo, H.

Chemistry - A European Journal Vol. 22 ( 12 ) page： 3956 - 3961 2016.3

Solubilization and Optical Tuning of Graphene Quantum Dots through Decarboxylative-Arylation Reviewed International journal

Oda Kazuma, Hiroto Satoru, SHinokubo Hiroshi

JSAP Annual Meetings Extended Abstracts Vol. 2016.1 ( 0 ) page： 3881 - 3881 2016.3

The synthesis of NiII and AlIII 10-azacorroles through coordination-induced cyclisation involving 1,2-migration Reviewed International journal

Omori, H., Hiroto, S., Shinokubo, H.

Chemical Communications Vol. 52 ( 17 ) page： 3540 - 3543 2016

NiII tetrahydronorcorroles: Antiaromatic porphyrinoids with saturated pyrrole units Reviewed International journal

Nozawa, R., Yamamoto, K., Hisaki, I., Shin, J.-Y., Shinokubo, H.

Chemical Communications Vol. 52 ( 44 ) page： 7106 - 7109 2016

Indolylindolinone: Easily accessible, tunable, and wide-range absorbing dyes Reviewed International journal

Shigeno, A., Matsuno, T., Hiroto, S., Shinokubo, H.

Chemistry Letters Vol. 44 ( 12 ) page： 1703 - 1705 2015.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.150815

Twisting of π-conjugated plane to one rotation Reviewed International journal

Hiroto S., Shinokubo H.

Kobunshi Vol. 64 ( 11 ) page： 713 - 714 2015.11

Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Kobunshi

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

A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin Reviewed International journal

Tanaka, Y., Yoneda, T., Furukawa, K., Koide, T., Mori, H., Tanaka, T., Shinokubo, H., Osuka, A.

Angewandte Chemie - International Edition Vol. 54 ( 37 ) page： 10908 - 10911 2015.9

Nitrogen-embedded buckybowl and its assembly with C[60] Reviewed International journal

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

Nature Communications Vol. 6 2015.9

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)

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

Nitrogen-embedded buckybowl and its assembly with C<inf>60</inf> Reviewed International journal

Yokoi, H., Hiraoka, Y., Hiroto, S., Sakamaki, D., Seki, S., Shinokubo, H.

Nature Communications Vol. 6 page： 8215 2015.9

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles Reviewed International journal

Nozawa, R., Yamamoto, K., Shin, J.-Y., Hiroto, S., Shinokubo, H.

Angewandte Chemie - International Edition Vol. 54 ( 29 ) page： 8454 - 8457 2015.7

Synthesis of highly twisted and fully π-conjugated porphyrinic oligomers Reviewed International journal

Ito, S., Hiroto, S., Lee, S., Son, M., Hisaki, I., Yoshida, T., Kim, D., Kobayashi, N., Shinokubo, H.

Journal of the American Chemical Society Vol. 137 ( 1 ) page： 142 - 145 2015.1

Palladium-catalyzed [3+2] annulation of meso-bromoporphyrins with silylacetylenes and desilylation of 8a-silyl-7,8-dehydropurpurin Reviewed International journal

Fukui, N., Arai, S., Shinokubo, H., Yorimitsu, H., Osuka, A.

Heterocycles Vol. 90 ( 1 ) page： 252 - 260 2015.1

Synthesis of Novel Porphyrinoids from Dipyrrins Invited Reviewed International journal

Hiroshi Shinokubo

Chemical Science of Electron Systems page： 243 - 255 2015.1

Authorship：Lead author,　Last author,　Corresponding author Language：English Publishing type：Part of collection (book) Publisher：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

Macrocyclic dipyrrin dimer bridged by ethylene and dioxyphenylene linkers Reviewed International journal

Ji-Young Shin, Satoru Hiroto, Hiroshi Shinokubo

Journal of Porphyrins and Phthalocyanines Vol. 19 ( 1-3 ) page： 135 - 139 2015

Isolation of a 1,4-diketone intermediate in oxidative dimerization of 2-hydroxyanthracene and its conversion to oxahelicene Reviewed International journal

Matsuno, T., Koyama, Y., Hiroto, S., Kumar, J., Kawai, T., Shinokubo, H.

Chemical Communications Vol. 51 ( 22 ) page： 4607 - 4610 2015

Diversity-oriented synthesis of tetrathia[8]circulenes by sequential C-H borylation and annulation Reviewed International journal

Kato, S., Serizawa, Y., Sakamaki, D., Seki, S., Miyake, Y., Shinokubo, H.

Chemical Communications Vol. 51 ( 95 ) page： 16944 - 16947 2015

A 3-pyridyl-5,15-diazaporphyrin nickel(II) complex as a bidentate metalloligand for transition metals Reviewed International journal

Yamaji, A., Shin, J.-Y., Miyake, Y., Shinokubo, H.

Angewandte Chemie - International Edition Vol. 53 ( 50 ) page： 13924 - 13927 2014.12

Synthesis of curved hexa-peri-hexabenzocoronenes Reviewed International journal

Yamaguchi, R., Hiroto, S., Shinokubo, H.

Chemistry Letters Vol. 43 ( 10 ) page： 1637 - 1639 2014.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.140577

Regioselective double cyclization of 5,15-bis(trimethylsilylethynyl)porphyrin to produce di(oxoethano)porphyrin Reviewed International journal

Oda, K., Hiroto, S., Shinokubo, H.

Chemistry Letters Vol. 43 ( 9 ) page： 1444 - 1446 2014.9

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.140470

Facile synthesis of nitrogen-containing polycyclic aromatic hydrocarbons from perylene bisimides Reviewed International journal

Ito, S., Hiroto, S., Shinokubo, H.

Chemistry Letters Vol. 43 ( 8 ) page： 1309 - 1311 2014.8

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Chemical Society of Japan

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

DOI： 10.1246/cl.140330

Synthesis of diazo-bridged bodipy dimer and tetramer by oxidative coupling of β-amino-substituted BODIPYs Reviewed International journal

Yokoi, H., Hiroto, S., Shinokubo, H.

Organic Letters Vol. 16 ( 11 ) page： 3004 - 3007 2014.6

Photodynamics of [26]- and [28]Hexaphyrin-Bodipy Hybrids Reviewed International journal

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 20 ( 16 ) page： 4574 - 4582 2014.4

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

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 515nm raised a band corresponding to the bodipy absorption. As the time delayed, the bodipy bands decreased and new absorption bands at 615 and 580nm 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 580nm 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.

DOI： 10.1002/chem.201400315

Silylethynyl substituents as porphyrin protecting groups for solubilization and selectivity control Reviewed International journal

Oda, K., Akita, M., Hiroto, S., Shinokubo, H.

Organic Letters Vol. 16 ( 6 ) page： 1818 - 1821 2014.3

An antiaromatic electrode-active material enabling high capacity and stable performance of rechargeable batteries Reviewed International journal

Shin, J.-Y., Yamada, T., Yoshikawa, H., Awaga, K., Shinokubo, H.

Angewandte Chemie - International Edition Vol. 53 ( 12 ) page： 3096 - 3101 2014.3

Synthesis of Novel Porphyrinoids through Organometallic Means Reviewed International journal

Shinokubo, H.

Journal of Synthetic Organic Chemistry Japan Vol. 72 ( 2 ) page： 149 - 157 2014.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Society of Synthetic Organic Chemistry, Japan

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

DOI： 10.5059/yukigoseikyokaishi.72.149

有機金属化学的手法による新規ポルフィリン類縁体の合成 Reviewed International journal

忍久保洋

有機合成化学協会誌 = Journal of synthetic organic chemistry, Japan Vol. 72 ( 2 ) page： 149 - 157 2014.2

Near-IR absorbing nickel(II) porphyrinoids prepared by regioselective insertion of silylenes into antiaromatic nickel(II) norcorrole International coauthorship International journal

Fukuoka, T., Uchida, K., Sung, Y.M., Shin, J.-Y., Ishida, S., Lim, J.M., Hiroto, S., Furukawa, K., Kim, D., Iwamoto, T., Shinokubo, H.

Angewandte Chemie - International Edition Vol. 126 ( 6 ) page： 1532 - 1535 2014.1

Transition metal catalyzed borylation of functional π-systems Reviewed International journal

Shinokubo, H.

Proceedings of the Japan Academy Series B: Physical and Biological Sciences Vol. 90 ( 1 ) page： 1 - 11 2014.1

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Japan Academy

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

DOI： 10.2183/pjab.90.1

Synthesis, reactivity and property of 5,15-dithiaporphyrin copper(II) complex Reviewed International journal

Wachi, N., Kondo, T., Ito, S., Hiroto, S., Shin, J.-Y., Shinokubo, H.

Journal of Porphyrins and Phthalocyanines Vol. 18 ( 8-9 ) page： 675 - 678 2014

Oxidation of 2-amino-substituted BODIPYs providing pyrazine-fused BODIPY trimers Reviewed International journal

Yokoi, H., Wachi, N., Hiroto, S., Shinokubo, H.

Chemical Communications Vol. 50 ( 21 ) page： 2715 - 2717 2014

Selective Synthesis of a [32]Octaphyrin(1.0.1.0.1.0.1.0) Bis(palladium) Complex by a Metal-Templated Strategy Reviewed International journal

Hiromitsu Kido, Ji-Young Shin, Hiroshi Shinokubo

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 52 ( 51 ) page： 13727 - 13730 2013.12

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

Hiromitsu Kido, Ji‐Young Shin, Hiroshi Shinokubo

Angewandte Chemie Vol. 125 ( 51 ) page： 13972 - 13975 2013.10

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley

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

DOI： 10.1002/ange.201306905

PubMed

Synthesis of Pyridine-Fused Perylene Imides with an Amidine Moiety for Hydrogen Bonding Reviewed International journal

Satoru Ito, Satoru Hiroto, Hiroshi Shinokubo

ORGANIC LETTERS Vol. 15 ( 12 ) page： 3110 - 3113 2013.6

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol401316q

Porphyrin Analogues That Consist of Indole, Benzofuran, and Benzothiophene Subunits Reviewed International journal

Shoichi Nakamura, Takeshi Kondo, Satoru Hiroto, Hiroshi Shinokubo

ASIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 2 ( 4 ) page： 312 - 319 2013.4

Functionalization of Hexa-peri-hexabenzocoronenes: Investigation of the Substituent Effects on a Superbenzene Reviewed International journal

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

CHEMISTRY-AN ASIAN JOURNAL Vol. 8 ( 1 ) page： 178 - 190 2013.1

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

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 S-0 -> S-1 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.

DOI： 10.1002/asia.201200723

Synthesis of highly distorted π-extended [2.2]metacyclophanes by intermolecular double oxidative coupling Reviewed International journal

Yutaro Koyama, Satoru Hiroto, Hiroshi Shinokubo

Angewandte Chemie - International Edition Vol. 52 ( 22 ) page： 5740 - 5743 2013

Language：Japanese Publishing type：Research paper (scientific journal)

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 &amp
Co. KGaA, Weinheim.

DOI： 10.1002/anie.201301180

Carbolithiation of meso-aryl-substituted 5,15-diazaporphyrin selectively provides 3-alkylated diazachlorins Reviewed International journal

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

Chemical Communications Vol. 49 ( 44 ) page： 5064 - 5066 2013

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry

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. © The Royal Society of Chemistry 2013.

DOI： 10.1039/c3cc41907j

Assembled structures of dipyrrins and their oligomers bridged by dioxy-boron moieties Reviewed International journal

Hiromitsu Maeda, Yuki Nishimura, Satoru Hiroto, Hiroshi Shinokubo

DALTON TRANSACTIONS Vol. 42 ( 45 ) page： 15885 - 15888 2013

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/c3dt50783a

meso-Thiaporphyrinoids Revisited: Missing of Sulfur by Small Metals Reviewed International journal

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 18 ( 50 ) page： 16129 - 16135 2012.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

Facile synthesis of meso-aryl-substituted 5,15-dithiaporphyrins and 10-thiacorroles has been achieved by sulfidation of a,a'-dichlorodipyrrin metal complexes with sodium sulfide in DMF. Thiacorrole metal complexes exhibit distinct aromaticity due to 18?p-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 PtII 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.

DOI： 10.1002/chem.201203255

Synthesis of Oxygen-Substituted Hexa-peri-hexabenzocoronenes through Ir-Catalyzed Direct Borylation Reviewed International journal

Ryuichi Yamaguchi, Satoru Hiroto, Hiroshi Shinokubo

ORGANIC LETTERS Vol. 14 ( 10 ) page： 2472 - 2475 2012.5

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

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 pi-extended quinone.

DOI： 10.1021/ol300743f

Synthesis of Nickel(II) Azacorroles by Pd-Catalyzed Amination of a,a'-Dichlorodipyrrin NiII Complex and Their Properties Reviewed International journal

Miki Horie, Yosuke Hayashi, Shigeru Yamaguchi, Hiroshi Shinokubo

CHEMISTRY-A EUROPEAN JOURNAL Vol. 18 ( 19 ) page： 5919 - 5923 2012.5

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

Synthesis of nickel(II) complexes of meso-aryl-substituted azacorroles was performed by BuchwaldHartwig amination of a dipyrrin NiII complex with benzylamine through C?N and C?C coupling. The highly planar structure of NiII azacorroles was elucidated by X-ray diffraction analysis. 1H NMR analysis and nucleus independent chemical shift (NICS) calculation on NiII azacorrole revealed its distinct aromaticity with [17]triaza-annulene 18p conjugation. In addition, acylation of azacorrole selectively afforded N- and C-acylated azacorroles depending on the reaction conditions, showing the dual reactivity of azacorroles.

DOI： 10.1002/chem.201200485

Energy and Electron Transfer from Fluorescent Mesostructured Organosilica Framework to Guest Dyes Reviewed International journal

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

LANGMUIR Vol. 28 ( 8 ) page： 3987 - 3994 2012.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

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 Forster 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.

DOI： 10.1021/la204645k

Facile Synthesis of Biphenyl-Fused BODIPY and Its Property Reviewed International journal

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

ORGANIC LETTERS Vol. 14 ( 3 ) page： 866 - 869 2012.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the beta-position of the BODIPY unit. The extended pi-system of the fused BODIPY induces near-infrared (NIR) absorption and strong pi-pi 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.

DOI： 10.1021/ol2033916

Ensemble and Single-Molecule Spectroscopic Study on Excitation Energy Transfer Processes in 1,3-Phenylene-Linked Perylenebisimide Oligomers Reviewed International journal

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

JOURNAL OF PHYSICAL CHEMISTRY B Vol. 116 ( 4 ) page： 1244 - 1255 2012.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

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-ylsubstituents 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 Forster-type energy hopping (EEH) times as compared with the EEH time constant (1.97 ps) calculated on the basis of the Forster 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.

DOI： 10.1021/jp208855u

Synthesis and oxidation of cyclic tetraindole Reviewed International journal

Shoichi Nakamura, Satoru Hiroto, Hiroshi Shinokubo

CHEMICAL SCIENCE Vol. 3 ( 2 ) page： 524 - 527 2012

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/c1sc00665g

Mesoporous Organosilica Hybrids Consisting of Silica-Wrapped p-p Stacking Columns Reviewed International journal

Norihiro Mizoshita, Takao Tani, Hiroshi Shinokubo, Shinji Inagaki

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 5 ) page： 1156 - 1160 2012

A meso-Spiro[Cyclopentadiene-Isoporphyrin] from a Phenylethynyl Porphyrin Platinum(II) Pincer Complex Reviewed International journal

Shoma Anabuki, Hiroshi Shinokubo, Naoki Aratani, Atsuhiro Osuka

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 13 ) page： 3174 - 3177 2012

Oxidative Annulation of ss-Aminoporphyrins into Pyrazine-Fused Diporphyrins Reviewed International journal

Masanari Akita, Satoru Hiroto, Hiroshi Shinokubo

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 12 ) page： 2894 - 2897 2012

Intermolecular Oxidative Annulation of 2-Aminoanthracenes to Diazaacenes and Aza[7]helicenes Reviewed International journal

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 41 ) page： 10333 - 10336 2012

Gram-Scale Synthesis of Nickel(II) Norcorrole: The Smallest Antiaromatic Porphyrinoid Reviewed International journal

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 51 ( 34 ) page： 8542 - 8545 2012

Functionalization of a Simple Dithienylethene via Palladium-Catalyzed Regioselective Direct Arylation Reviewed International journal

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

ORGANIC LETTERS Vol. 13 ( 24 ) page： 6394 - 6397 2011.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol2026069

A Hexameric Porphyrin Triangle Constructed by Suzuki-Miyaura Cross-coupling Reaction Reviewed International journal

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

CHEMISTRY LETTERS Vol. 40 ( 9 ) page： 902 - 903 2011.9

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：CHEMICAL SOC JAPAN

A meso-to-beta directly linked hexameric porphyrin triangle was synthesized by the Suzuki-Miyaura cross-coupling reaction via either one-pot or a stepwise route. Hexakis-zine(II) complex of the porphyrin triangle exhibits a split Soret band in the absorption spectrum, reflecting the effective exciton coupling over the whole molecule.

DOI： 10.1246/cl.2011.902

Synthetic Protocol for Diarylethenes through Suzuki-Miyaura Coupling Reviewed

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

Chem. Commun. Vol. 47 ( 25 ) page： 7149-7151 2011.5

Synthesis of Directly Connected BODIPY Oligomers through Suzuki-Miyaura Coupling Reviewed

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

Org. Lett. Vol. 13 ( 12 ) page： 2992-2995 2011.5

Iridium-Catalyzed Direct Tetraborylation of Perylene Bisimides Reviewed

Takuro Teraoka, Satoru Hiroto, and Hiroshi Shinokubo

Org. Lett. Vol. 13 ( 10 ) page： 2532-2535 2011.4

Metal-Mediated Synthesis of Antiaromatic Porphyrinoids from a BODIPY Precursor Reviewed

Takafumi Sakida, Shigeru Yamaguchi, and Hiroshi Shinokubo

Angew. Chem., Int. Ed. Vol. 50 ( 10 ) page： 2280-2283 2011.2

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

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

Chem. Sci. Vol. 2 ( 4 ) page： 748-751 2011.1

Peripherally Cyclometalated Iridium Complexes of Dipyridylporphyrin Reviewed

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

Dalton Trans. page： in press 2011

Synthesis of a Diimidazolylporphyrin Pincer Palladium Complex Reviewed

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

J. Porphyrins Phthalocyanines page： in press 2011

Pyrrole-Bridged Porphyrin Nanorings Reviewed

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

Chem. Eur. J. Vol. 16 ( 45 ) page： 13320-13324 2010.11

A Porphyrin Nanobarrel that Encapsulates C60 Reviewed

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

J. Am. Chem. Soc. Vol. 132 ( 46 ) page： 16356-16357 2010.10

Platinum(II) and Platinum(IV) Porphyrin Pincer Complexes: Synthesis, Structures, and Reactivity Reviewed International journal

Keita Yoshida, Shigeru Yamaguchi, Atsuhiro Osuka, Hiroshi Shinokubo

ORGANOMETALLICS Vol. 29 ( 17 ) page： 3997 - 4000 2010.9

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Pt(II)and Pt(IV)porphyrin pincer complexes were synthesized and characterized. Their structures and electronic properties were influenced by the valence state of platinum at the outer coordination site. The considerable distortion in the porphyrin core of the Pt(II) complex was relieved in the Pt(IV) complex, due to the change of the coordination geometry of platinum. Oxidation of the phenylplatinum(II) pincer complex with iodine induced a facile carbon carbon bond formation reaction at the meso position via reductive elimination.

DOI： 10.1021/om100644n

Directly Pd(II)-Bridged Porphyrin Belts with Remarkable Curvatures Reviewed

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

J. Am. Chem. Soc. Vol. 132 ( 34 ) page： 11868-11869 2010.9

eta(2)-Porphyrin Ru(II) pi Complexes Reviewed International journal

Shigeru Yamaguchi, Hiroshi Shinokubo, Atsuhiro Osuka

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 132 ( 29 ) page： 9992 - 9993 2010.7

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Highly stable eta(2)-porphyrin Ru(II) pi complexes have been synthesized. The formation of the eta(2) pi it bond has been facilitated through pi-pi stacking interactions between the porphyrin and the planar ligand on Ru. pi coordination of ruthenium to porphyrin results in dramatic changes in the aromaticity and electronic properties. These properties are controllable via fine-tuning of the ligand on ruthenium.

DOI： 10.1021/ja104842h

A Stable Non-Kekule Singlet Biradicaloid from meso-Free 5,10,20,25-Tetrakis(Pentafluorophenyl)-Substituted [26]Hexaphyrin(1.1.1.1.1.1) Reviewed International journal

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 132 ( 21 ) page： 7246 - + 2010.6

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

A meso,meso-diketohexaphyrin was isolated and characterized as a chemically stable non-Kekule singlet biradicaloid. Two unpaired electrons are seemingly delocalized on two tripyrrolic units separated by C=O bonds. These results underscore the potential of expanded porphyrins to achieve unique electronic states.

DOI： 10.1021/ja101040s

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

Chihiro Maeda, Hiroshi Shinokubo, and Atsuhiro Osuka

Org. Lett. Vol. 12 ( 8 ) page： 1820-1823 2010.4

Porphyrin "Lego Block" Strategy To Construct Directly meso-beta Doubly Linked Porphyrin Rings Reviewed

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

Angew. Chem., Int. Ed. Vol. 49 ( 21 ) page： 3617-3620 2010.4

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

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

Chem. Eur. J. Vol. 16 ( 17 ) page： 5052-5061 2010.3

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

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

J. Phys. Chem. A Vol. 114 ( 10 ) page： 3384-3390 2010.3

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

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

Chem. Eur. J. Vol. 16 ( 10 ) page： 3009-3012 2010.2

Bithiophene-Porphyrin Hybrid Nanorings Reviewed

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

Chem. Asian J. Vol. 5 ( 4 ) page： 764-767 2010.1

A Stable Organic Radical Delocalized on a Highly Twisted pi System Formed Upon Palladium Metalation of a Mobius Aromatic Hexaphyrin Reviewed International journal

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 49 ( 8 ) page： 1489 - 1491 2010

Doubly beta-Functionalized Meso-Meso Directly Linked Porphyrin Dimer Sensitizers for Photovoltaics Reviewed International journal

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

JOURNAL OF PHYSICAL CHEMISTRY C Vol. 113 ( 52 ) page： 21956 - 21963 2009.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Novel meso-meso directly linked porphyrin dinners tethered at beta-pyrrolic positions of the porphyrin ring with 2-propenoic acids or 2,4-pentadienoic acids were prepared for sensitization of nanocrystalline titanium dioxide solar cells. Most importantly, the absorption spectra of dimeric porphyrins were notably extended into the midvisible region in the solar spectrum while the LUMO levels are sufficiently high to inject electrons to the conduction band of TiO2. Among these dimers, PEG-2b-bd-Zn2 dimer, bearing a poly(ethylene glycol) end group at one meso position, showed the highest incident photon-to-photocurrent generation with 47% efficiency at the Soret region as well as the power conversion efficiency of 4.2% under standard AM 1.5 solar condition. To elucidate electronic structures and excited-state properties, UV-vis absorption and emission, cyclic voltammetry measurements, and density functional theory Calculations were performed. To Our best knowledge, the obtained conversion efficiency of 4.2% from PEG-2b-bd-Zn2-sensitized DSSC is the highest photovoltaic performance among DSSCs based on oligomeric porphyrins. Thus, this work suggests that the wide spectral response of directly linked porphyrin dimers due to the excitonic coupling is an intriguing aspect of directly linked pophyrin dimers to be utilized for DSSCs and gives an insight into the design of more efficient light-harvesting molecules.

DOI： 10.1021/jp905675x

Synthesis of Arylated Perylene Bisimides through C-H Bond Cleavage under Ruthenium Catalysis Reviewed

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

Org. Lett. Vol. 11 ( 23 ) page： 5426-5429 2009.12

meso,meso '-Bis(5-azaindol-2-yl)-Appended meso-meso-Linked Zn(II) Diporphyrin: A Discrete Fluorescent Assembly Reviewed International journal

Chihiro Maeda, Hiroshi Shinokubo, Atsuhiro Osuka

ORGANIC LETTERS Vol. 11 ( 22 ) page： 5322 - 5325 2009.11

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Cu(II)-catalyzed intramolecular cyclization of meso-(4-aminopyrid-3-yl)ethynyl Zn(II) porphyrin provided meso-(5-azaindol-2-yl)-substituted Zn(II) porphyrin. meso,meso'-Bis(5-azaindol-2-yl)-substituted diporphyrin 7 was similarly prepared and was found to form a fluorescent trimeric prismatic assembly consisting of single atropisomer 7(in-in).

DOI： 10.1021/ol902294r

Palladium-Catalyzed Dimerization of meso-Bromoporphyrins: Highly Regioselective meso-beta Coupling through Unprecedented Remote C-H Bond Cleavage Reviewed International journal

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

CHEMISTRY-A EUROPEAN JOURNAL Vol. 15 ( 45 ) page： 12208 - 12211 2009.10

Regioselective Ru-Catalyzed Direct 2,5,8,11-Alkylation of Perylene Bisimides Reviewed

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

Chem. Eur. J. Vol. 15 ( 31 ) page： 7530-7533 2009.7

Porphyrin Derivatives with Carbon-Metal Bonds Reviewed

Satoru Hiroto, Shigeru Yamaguchi, Hiroshi Shinokubo, and Atsuhiro Osuka

J. Synth. Org. Chem. Jpn. Vol. 67 ( 7 ) page： 688-700 2009.7

Unusual Interchromophoric Interactions in beta,beta ' Directly and Doubly Linked Corrole Dimers: Prohibited Electronic Communication and Abnormal Singlet Ground States Reviewed International journal

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 131 ( 18 ) page： 6412 - 6420 2009.5

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Directly and doubly beta,beta'-linked corrole dimers (DH3CD, DH2CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H3CM and the singly beta,beta'-linked corrole dimer SH3CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dinners, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH3CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH2CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic pi-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH2CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH2CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH3CD. Collectively, double beta,beta'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.

DOI： 10.1021/ja900220y

Bis-rhodium hexaphyrins: metalation of [28]hexaphyrin and a smooth Huckel aromatic-antiaromatic interconversion Reviewed International journal

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

CHEMICAL COMMUNICATIONS ( 25 ) page： 3762 - 3764 2009.5

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

Metalation of [28]hexaphyrin(1.1.1.1.1.1) with [RhCl(CO)(2)](2) resulted in the formation of an antiaromatic bis-Rh(I) complex, which can be oxidized to an aromatic bis-Rh(I) complex with retention of its rectangular structure.

DOI： 10.1039/b905859a

Functionalization of Boron Dipyrrin (BODIPY) Dyes through Iridium and Rhodium Catalysis: A Complementary Approach to alpha- and beta-Substituted BODIPYs Reviewed International journal

Jinping Chen, Masatoshi Mizumura, Hiroshi Shinokubo, Atsuhiro Osuka

CHEMISTRY-A EUROPEAN JOURNAL Vol. 15 ( 24 ) page： 5942 - 5949 2009.5

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

Iridium-catalyzed direct borylation has been applied to meso-substituted dipyrromethane and boron dipyrrin (BODIPY) dyes. Borylation is highly regioselective and complementary: it occurs exclusively at the alpha position for meso-mesityldipyrromethane and at the beta positions for meso-mesityl BODIPY dye. This regioselective borylation enables a variety of alpha- and beta-substituted BODIPY dyes to be synthesized. Introduction of alpha,beta-enoate and alpha,beta,gamma,delta-dienoate functions into BODIPY dyes at the alpha or beta positions was achieved by rhodium-catalyzed Heck-type addition of the borylated compounds to acrylate and 2,4-pentadienoate esters. This functionalization has a significant effect on the electronic properties of BODIPY dyes, as seen in substantial redshift of the absorption and emission spectra. Comparative studies showed that the alpha- and beta-substituted series of BODIPY dyes show substantially different photophysical properties, and thus the importance of the position to be functionalized is highlighted.

DOI： 10.1002/chem.200802541

Metathesis-like Splitting Reactions of Metallated [36]Octaphyrins(1.1.1.1.1.1.1.1): Experimental and Computational Investigations Reviewed International journal

Yasuo Tanaka, Hiroshi Shinokubo, Yosuke Yoshimura, Atsuhiro Osuka

CHEMISTRY-A EUROPEAN JOURNAL Vol. 15 ( 23 ) page： 5674 - 5685 2009.4

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

meso-Octakis(pentafluorophenyl)-substituted [36]octaphyrin(1.1.1.1.1.1.1.1) (1) is a figure-of-eight nonaromatic macrocycle that serves its a unique platform to induce a metathesis-like splitting reaction upon bis-Cu(II) metalation. To get a better understanding of this splitting reaction, we examined the metalation of 1 with several metal ions. In contrast with the smooth and quantitative splitting reaction of bis-Cu(II) complex 1-CuCu, free-base 1, mono-Cu(II) complex 1-Cu, and bis-Zi(II) complex 1-ZnZn do not undergo the splitting reaction. Mono-Con complex 1-Co was selectively produced from metalation with the Co(II) ion, from which hybrid complex 1-CoCu was synthesized. The hybrid complex 1-CoCu undergoes the splitting reaction to give 2-Co and 2-Cu quantitatively. Activation parameters of the splitting reactions were determined: E(a) = 104 kJ mol(-1), Delta H double dagger 101 kJ mol(-1), Delta S double dagger = -25.0 J mol(-1) K(-1), and Delta V double dagger = 18 cm(3)mol(-1) for 1-CuCu and E(a) = 105 kJ mol(-1), Delta H double dagger = 102 kJ mol(-1), and Delta S double dagger = -29.9 J mol(-1) K(-1) for 1-CoCu. A marked difference between the splitting reaction reactivity of 1-CuCu and 1-ZnZn has been examined by DFT calculations at the B3LYP/631SDD// B3LYP/LANL2DZ level, which revealed that the reaction proceeds through it stepwise route involving initial C1-C20 bond formation to give INT1 as the rate-determining step and subsequent C21-C40 bond formation to give a spirocyclobutane intermediate (INT2), followed by a radical reverse cycloaddition reaction to give two metalloporphyrins. Inherent instability of 1-CuCu, which may arise from its strongly distorted structure, was indicated to be a main factor in the smooth splitting reaction. Finally, a new bis-Pd(II) complex (5-PdPd) was isolated in the metalation of 1 with Pd(OAc)(2) in a 9:1 mixture of 2,2,2-trifluoroethanol and methanol as a manifestation of the transannular electronic interaction in metalated octaphyrin complexes. Collectively, these results underscore the importance of the transannular electronic interactions that are enhanced by metalation, depending upon the coordinated metal ions.

DOI： 10.1002/chem.200900454

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

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

J. Phys. Chem. B, Vol. 113 ( 17 ) page： 5794–5802 2009.4

Post-Modification of meso-meso-Linked Porphyrin Arrays by Iridium and Rhodium Catalyses for Tuning of Energy Gap Reviewed International journal

Jinping Chen, Naoki Aratani, Hiroshi Shinokubo, Atsuhiro Osuka

CHEMISTRY-AN ASIAN JOURNAL Vol. 4 ( 7 ) page： 1126 - 1133 2009.3

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

meso-meso-Linked diporphyrins fabricated with multiple unsaturated carboxylic acid groups are efficiently synthesized by the use of transition-metal catalysis. Iridium-catalyzed direct borylation of meso-meso-linked diporphyrins furnish multi-borylated diporphyrins with high regioselectivity. Then, the introduction of alpha,beta- or alpha,beta,gamma,delta-unsaturated ester functions to the diporphyrins is achieved through rhodium-catalyzed Heck-type addition of the borylated diporphyrins to acrylate or 2,4-pentadienoate esters. Saponification of the esters to the corresponding acids is accomplished in high yields. The post-modification of diporphyrin 6 smoothly provides a water-soluble multiporphyrin array 1 in 84% total yield in 3 steps. This functionalization significantly affects the electronic properties of the porphyrins, resulting in different energy levels of each porphyrin unit. The absorption and fluorescence spectra indicate efficient energy transfer in the porphyrin dimers.

DOI： 10.1002/asia.200900053

First self-assembly study of large pi-conjugated corrole dimers on solid substrates Reviewed International journal

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

APPLIED SURFACE SCIENCE Vol. 255 ( 11 ) page： 5885 - 5890 2009.3

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE BV

Our study focus on beta, beta'-doubly linked corrole dimers (CDs) on mica and Au(1 1 1) surface using samples prepared by the synthetic method described by Osuka group appeared on recent publication [S. Hiroto, K. Furukawa, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 128 (2006) 12380]. Atomic force microscopy (AFM) and scanning tunneling microscopy (STM) were used to investigate the self-assembled structure of corrole dimers adsorbed on mica and Au(1 1 1) surfaces respectively at room temperature in air. The CDs adopt a dissimilar adsorption modality due to the different surface free energy of the different substrates. These types of molecular layers provide a useful platform for the study of surface and interface phenomena outside a vacuum system. It is potentially useful for practical fabrication of molecular devices because of the simplicity of the sample preparation and the stability of the interface in ambient conditions. (C) 2009 Elsevier B. V. All rights reserved.

DOI： 10.1016/j.apsusc.2009.01.026

Adsorption characteristic of self-assembled corrole dimers on HOPG Reviewed International coauthorship International journal

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

SURFACE AND INTERFACE ANALYSIS Vol. 41 ( 3 ) page： 225 - 230 2009.3

Language：English Publishing type：Research paper (scientific journal) Publisher：WILEY

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

DOI： 10.1002/sia.3011

Zwitterionic Corroles: Regioselective Nucleophilic Pyridination of a Doubly Linked Biscorrole Reviewed International journal

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 48 ( 13 ) page： 2388 - 2390 2009.2

Double Cleavage of sp(2) C-H and sp(3) C-H Bonds on One Metal Center: DMF-Appended Cyclometalated Platinum(II) and -(IV) Porphyrins Reviewed International journal

Shigeru Yamaguchi, Hiroshi Shinokubo, Atsuhiro Osuka

INORGANIC CHEMISTRY Vol. 48 ( 3 ) page： 795 - 797 2009.2

Adsorption Characteristic of Self-Assembled Corrole Dimers on HOPG Reviewed

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

Surf. Interface Anal. Vol. 41 page： 225–230 2009.1

Synthesis of Norbornane-Bridged Diporphyrins via Palladium-Catalyzed [3+2] Annulation Strategy Reviewed International journal

Masatoshi Mizumura, Hiroshi Shinokubo, Atsuhiro Osuka

SYNTHESIS-STUTTGART ( 1 ) page： 59 - 61 2009.1

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：GEORG THIEME VERLAG KG

The reaction of meso-bromoporphyrins with norbornene-fused porphyrins afforded novel norbornane-bridged diporphyrins in excellent yields via palladium-catalyzed [3+2] annulation reaction.

DOI： 10.1055/s-0028-1083267

Marriage of porphyrin chemistry with metal-catalysed reactions Reviewed International journal

Hiroshi Shinokubo, Atsuhiro Osuka

CHEMICAL COMMUNICATIONS ( 9 ) page： 1011 - 1021 2009

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

The development of porphyrin synthesis by means of transition metal-catalyzed reactions is explored in this feature article. Porphyrins have been receiving much attention in a wide area of chemistry as functional dyes, non-linear optical materials, ligands for a variety of metals, structural motifs in supramolecules, and so forth. However, they have been merely recognized as a reaction substrate in transition metal-catalyzed transformations. Recently, application of such new methodologies to porphyrin synthesis has proven to be very powerful to create new types of porphyrinic compounds, which have their own intriguing structures and properties. New transformations on porphyrins via transition metal catalysis offer us prospects of new designs of architectures, thus facilitating further development of this important class of functional molecules.

DOI： 10.1039/b817941g

Synthesis of a pyridine-fused porphyrinoid: oxopyridochlorin Reviewed International journal

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

CHEMICAL COMMUNICATIONS ( 9 ) page： 1028 - 1030 2009

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

The treatment of 3,5-dibenzoylporphyrins with ammonium acetate provided novel oxopyridochlorins as the first examples of pyridine-fused porphyrinoids, which displayed absorption bands reaching into the near IR region and an ability to sensitize singlet oxygen effectively.

DOI： 10.1039/b819284g

Synthesis of bithiophene-bridged cyclic porphyrin arrays Reviewed International journal

Osawa Kenta, Song Jianxin, Aratani Naoki, Shinokubo Hiroshi, Osuka Atsuhiro

Abstracts of Symposium on Physical Organic Chemistry Vol. 2009 ( 0 ) page： 242 - 242 2009

Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Society of Physical Organic Chemistry, Japan

In most of cases the linkage of cyclic porphyrin arrays have been limited to phenylene- or ethynylene-bridges. Here we report the synthesis of novel cyclic porphyrin arrays including 2,2-bithiophene as a meso-to-meso spacer unit. The 1H-NMR spectra displayed the almost same chemical shifts for these cyclic porphyrin arrays except the slight shifts of thiophene proton, indicating high symmetric cyclic structure of them in solution. On the other hand, the X-ray diffraction analysis revealed the solid-state structure of cyclic 3mer Zn(II) complex which showed, to our surprise, the asymmetric conformation in which two of the bithiophene units were syn isomer and one of them was anti isomer. This isomerization of spacer units causes the molecule to apparently bend.

DOI： 10.11494/kisoyuki.2009.0.242.0

Synthesis of Directly and Doubly Linked Dioxoisobacteriochlorin Dimers Reviewed International journal

Satoru Hiroto, Ichiro Hisaki, Hiroshi Shinokubo, Atsuhiro Osuka

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 130 ( 48 ) page： 16172 - 16173 2008.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Oxidation of 2,18-diborylporphyrin provided 2,18-dihydroxyporphyrin, which shows solvent-dependent keto-enol tautomerism and dimerization through hydrogen bonding interaction in solution. Further oxidation of 2,18-dihydroxyporphyrins afforded doubly and directly linked dioxoisobacteriochlorin face-to-face dimers.

DOI： 10.1021/ja807659h

Pt(II)- and Pt(IV)-Bridged Cofacial Diporphyrins via Carbon-Transition Metal sigma-Bonds Reviewed International journal

Shigeru Yamaguchi, Taisuke Katoh, Hiroshi Shinokubo, Atsuhiro Osuka

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 130 ( 44 ) page： 14440 - + 2008.11

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

A directly Pt(IV)-bridged cofacial diporphyrin has been synthesized by the cyclometalation reaction of beta-pyridylporphyrin with a Pt(IV) salt. Upon treatment with methylhydrazine, the Pt(IV) bridge is reduced to the Pt(II) center, resulting in a Pt(II)-bridged cofacial dimer with a helicity inversion of the complex as well as change in eletronic communication through the metal bridge.

DOI： 10.1021/ja8066385

Unambiguous identification of Mobius aromaticity for meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) Reviewed International journal

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 130 ( 41 ) page： 13568 - 13579 2008.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism spectroscopy, and single-crystal X-ray diffraction analysis. All of these data consistently indicate that [28]hexaphyrins(1.1.1.1.1.1) in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Mobius conformations with distinct aromaticities, with a small contribution from a planar rectangular conformation with antiaromatic character at slightly higher energy. In the solid state, [28]hexaphyrins(1.1.1.1.1.1) take either planar or Mobius-twisted conformations, depending upon the meso-aryl substituents and crystallization conditions, indicating a small energy difference between the two conformers. Importantly, when the temperature is decreased to -100 degrees C in THF, these rapid interconversions among Mobius conformations are frozen, allowing the detection of a single [28]hexaphyrin(1.1.1.1.1.1) species having a Mobius conformation. Detailed analyses of the solid-state Mobius structures of compounds 2b, 2c, and 2f showed that singly twisted structures are achieved without serious strain and that cyclic pi-conjugation is well-preserved, as needed for exhibiting strong diatropic ring currents. Actually, the harmonic-oscillator model for aromaticity (HOMA) values of these structures are significantly large (0.85, 0.69, and 0.71, respectively), confirming the first demonstration of stable Mobius aromatic systems consisting of free-base expanded porphyrins without the assistance of metal coordination.

DOI： 10.1021/ja801983d

Photoelectrochemical Properties of Doubly beta-Functionalized Porphyrin Sensitizers for Dye-Sensitized Nanocrystalline-TiO2 Solar Cells Reviewed International journal

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

JOURNAL OF PHYSICAL CHEMISTRY C Vol. 112 ( 42 ) page： 16691 - 16699 2008.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Functionalized porphyrins at meso- and beta-positions with different carboxylic acid groups were prepared to investigate electronic and photovoltaic properties as dye-sensitized nanocrystalline-TiO2 solar cells. The electronic structures of the porphyrin macrocyclic core are strongly coupled with olefinic side chains so that the absorption spectrum exhibits largely broad and red-shifted Soret and Q-bands, especially up to 475 nm at the Soret band in a porphyrin doubly functionalized with malonic diacid groups. Among porphyrin derivatives prepared in this study, 2b-bdta-Zn exhibits the maximum overall conversion efficiency of 3.03% and the maximum incident photon to current efficiency of 60. 1% in the Soret band region, superior to the others. From such photovoltaic performances, we can suggest that multiple pathways through olefinic side chains at two beta-positions enhance the overall electron injection efficiency and the moderate distance between the porphyrin sensitizer and the TiO2 semiconductor layer is important, retarding the charge recombination processes. As a consequence, these combined effects give rise to higher photovoltaic efficiency in photovoltaic regenerative solar cells.

DOI： 10.1021/jp804258q

2,5-Thienylene-Bridged Triangular and Linear Porphyrin Trimers Reviewed

Jianxin Song, So Young Jang, Shigeru Yamaguchi, Jeyaraman Sankar, Satoru Hiroto, Naoki Aratani, Jae-Yoon Shin, Shanmugam Easwaramoorthi, Kil Suk Kim, Dongho Kim, Hiroshi Shinokubo, and Atsuhiro Osuka

Angew. Chem., Int. Ed. Vol. 47 page： 6004-6007 2008.7

Synthesis of Novel Chiral Porphyrins through Pd-Catalyzed [3 + 2] Annulation and Heterochiral Self-Assembling to Form Heterodimers Reviewed

Masatoshi Mizumura, Hiroshi Shinokubo, and Atsuhiro Osuka

Angew. Chem., Int. Ed. Vol. 47 page： 5387-5381 2008.6

Highly selective Ir-catalyzed direct sixfold borylation of peripheral aromatic substituents on hexakisaryl-substituted [28]hexaphyrin(1.1.1.1.1.1) Reviewed International journal

Goro Mori, Hiroshi Shinokubo, Atsuhiro Osuka

TETRAHEDRON LETTERS Vol. 49 ( 13 ) page： 2170 - 2172 2008.3

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：PERGAMON-ELSEVIER SCIENCE LTD

Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by Ir-catalyzed borylation with the Smith-Miyaura-Hartwig protocol. High para. selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenyl substituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrin without borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylated hexaphyrin can be used for Suzuki-Miyaura cross-coupling reaction. (c) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.01.069

Highly selective Ir-catalyzed direct sixfold borylation of peripheral aromatic substituents on hexakisaryl-substituted [28]hexaphyrin(1.1.1.1.1.1) Reviewed International journal

Mori Goro, Shinokubo Hiroshi, Osuka Atsuhiro

Tetrahedron Letters Vol. 49 ( 13 ) page： 2170 - 2172 2008.3

Authorship：Corresponding author Language：English Publishing type：Research paper (scientific journal)

Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by iridium-catalyzed borylation with theSmith–Miyaura–Hartwig protocol. High para selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenylsubstituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrinwithout borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylatedhexaphyrin can be used for Suzuki–Miyaura cross coupling reaction.

Dimeric assemblies from 1 2,3-triazole-appended Zn(II) porphyrins with control of NH-tautomerism in 1 2,3-triazole Reviewed International journal

Chihiro Maeda, Shigeru Yamaguchi, Chusaku Ikeda, Hiroshi Shinokubo, Atsuhiro Osuka

ORGANIC LETTERS Vol. 10 ( 4 ) page： 549 - 552 2008.2

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Cu(I)-catalyzed 1,3-dipolar cycloaddition of meso-ethynyl Zn(II) porphyrin with benzyl azide efficiently provides meso-1-benzyl-1H-1,2,3-triazolyl Zn(II) porphyrin, which assembles to form a slipped cofacial dimer by the complementary coordination of the triazole nitrogen atom at the 3-position to the zinc center of a second porphyrin moiety both in the solid and solution states. Removal of the benzyl protection and introduction of a 2-ethoxycarbonylphenyl moiety greatly stabilize the dimeric assembly through an additional hydrogen bonding interaction between the NH proton of 2H-1,2,3-triazole and the carbonyl oxygen.

DOI： 10.1021/ol7028299

meso-Aryl Substituted Rubyrin and Its Higher Homologues: Structural Characterization and Chemical Properties Reviewed

Soji Shimizu, Shohei Saito, Won-Seob Cho, Jonathan L. Sessler, Hiroshi Shinokubo, and Atsuhiro Osuka

Chem. Eur. J. Vol. 14 ( 9 ) page： 2668-2678 2008.2

Efficient Rhodium-Catalyzed installation of unsaturated ester functions onto porphyirins: Site-specific heck-type addition versus conjugate addition Reviewed International journal

Hiromi Baba, Jinping Chen, Hiroshi Shinokubo, Atsuhiro Osuka

CHEMISTRY-A EUROPEAN JOURNAL Vol. 14 ( 14 ) page： 4256 - 4262 2008

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：WILEY-V C H VERLAG GMBH

A facile introduction of alpha,beta-or alpha,beta,gamma,delta-unsaturated ester functions onto porphyrins was achieved through rhodium-catalyzed addition of beta-borylporphyrins to acrylate or 2,4-pentadienoate esters. The reaction of meso-borylporphyrins with acrylates exclusively afforded saturated esters by 1,4-conjugate addition under the same re-mode (Heck-type versus conjugate addition) is highly dependent on the reaction site (beta versus meso). This functionalization has a significant impact on the electronic properties of the pi system of porphyrins, which induces a substantial redshift and broadening in the absorption spectra by effective conjugation through the beta positions. The coplanar structure of the unsaturated ester moieties with respect to the porphyrin core has been unambiguously elucidated by X-ray crystallographic analysis.

DOI： 10.1002/chem.200701943

Metalation of expanded porphyrins: A chemical trigger used to produce molecular twisting and Mobius aromaticity Reviewed International journal

Yasuo Tanaka, Shohei Saito, Shigeki Mori, Naoki Aratani, Hiroshi Shinokubo, Naoki Shibata, Yoshiki Higuchi, Zin Seok Yoon, Kil Suk Kim, Su Bum Noh, Jong Kang Park, Dongho Kim, Atsuhiro Osuka

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 47 ( 4 ) page： 681 - 684 2008

Synthesis of chiral porphyrins through Pd-catalyzed [3+2] annulation and heterochiral self-assembly Reviewed International journal

Masatoshi Mizumura, Hiroshi Shinokubo, Atsuhiro Osuka

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 47 ( 29 ) page： 5378 - 5381 2008

Unambiguous Identification of Mobius Aromaticity for meso-Aryl-Substituted [28]Hexaphyrins (1. 1. 1. 1. 1. 1) Reviewed International journal

HARAPRIYA Rath, 忍久保洋, 小林長夫

J. Am Chem. Soc. 130 page： 13568 - 13579 2008

Synthesis and Characterization of Pyridine-fused Porpyrinoid Reviewed International journal

Tokuji Sumito, Shinokubo Hiroshi, Osuka Atsuhiro

Abstracts of Symposium on Physical Organic Chemistry Vol. 2008 ( 0 ) page： 51 - 51 2008

Authorship：Corresponding author Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Society of Physical Organic Chemistry, Japan

The introduction of fused π-conjugated segments to porphyrin is expected to create a variety of conjugated porphyrin systems that would exhibit unique optical and electrochemical properties. We have previously reported the formation of dehydropurpurin from meso-bromoporphyrins in the presence of palladium catalyst and its conversion into 3,5-dibenzoylporphyrin by oxidation of the outer C-C double bond. This time we have found that pyridine-fused porphyrinoid was formed by the reaction of 3,5-dibenzoylporphyrin with ammonium acetate. The framework of this compound contains pyridine and carbonyl moieties. X-Ray crystallographic analysis unambiguously elucidated its structure. Both its structure and optical property will be presented.

DOI： 10.11494/kisoyuki.2008.0.51.0