Faculty Profiles - SHINOKUBO, Hiroshi

Papers - SHINOKUBO, Hiroshi

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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

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

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

Satoshi Kato, Kazuki Miwa, Hideaki Takano, Hiroshi Shinokubo

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

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

Web of Science

Scopus

PubMed

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

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

Hiroshi Shinokubo

Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry Vol. 83 ( 5 ) page： 455 - 463 2025

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

Fukui N., Shinokubo H.

Yuki Gosei Kagaku Kyokaishi Journal of Synthetic Organic Chemistry Vol. 83 ( 5 ) page： 455 - 463 2025

Authorship：Corresponding author Language：English 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

Scopus

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

Web of Science

Scopus

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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

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

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Papers - SHINOKUBO, Hiroshi