Faculty Profiles - SHINOKUBO, Hiroshi

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

CiNii Research

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