論文 - 福井　識人

Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism 査読有り

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

JACS Au     2025年3月

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

DOI： 10.1021/jacsau.5c00037

Constructing Figure-Eight Structures by Inner-Bond Cleavage 招待有り 査読有り

Norihito Fukui

Synlett     2025年1月

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担当区分：筆頭著者,　最終著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Georg Thieme Verlag KG  

Contemporary synthetic strategies in organic chemistry rely heavily on the stepwise formation of bonds between constituent fragments of the target compound, namely the bottom-up approach. However, this dependency poses significant challenges for the preparation of several classes of complex molecules, such as figure-eight molecules, despite their desirable functionality in advanced materials. Recently, we have developed an oxidative inner-bond-cleavage approach that enables a salable, catalytic, and enantioselective synthesis of figure-eight aromatic macrocycles. This Synpacts article summarizes the background, results, and outlook of our achievement. 1Introduction2Background3Our Contribution4Conclusion and Outlook

DOI： 10.1055/a-2529-5812

Synthesis and Properties of Donor–Acceptor‐Type Cyclobisbiphenylenecarbonyls 査読有り

Emiko Nishimoto, Tomoyuki Ikai, Hiroshi Shinokubo, Norihito Fukui

Chemistry – A European Journal   31 巻 ( 15 )   2025年1月

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

Abstract

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 |g_CPL| 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 |g_CPL| values.

DOI： 10.1002/chem.202404194

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

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

Journal of Materials Chemistry C   13 巻   頁： 655 - 662   2024年10月

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

We have applied the dual incorporation of imide substituents and imine-type nitrogen atoms to anthracene, and thus synthesized phenazine bisimide. The structure–property relationship of this design strategy was systematically investigated.

DOI： 10.1039/d4tc03306j

Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons 査読有り

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

Journal of the American Chemical Society   146 巻 ( 43 ) 頁： 29383 - 29390   2024年9月

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

DOI： 10.1021/jacs.4c07985

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

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

Journal of the American Chemical Society   146 巻 ( 23 ) 頁： 16332 - 16339   2024年5月

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

DOI： 10.1021/jacs.4c05358

Synthesis of sterically congested double helicene by alkyne cycloisomerization 招待有り 査読有り

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

Chemical Communications   60 巻 ( 47 ) 頁： 6035 - 6038   2024年5月

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

ナフタレンモノイミドをビルディングブロックとする含典型元素機能性π共役分子の開発 招待有り

田島 慶太, 福井 識人, 忍久保 洋

TCIメール   43 巻   頁： 2 - 12   2024年3月

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Excimer Formation Driven by Excited-State Structural Relaxation in a Covalent Aminonaphthalimide Dimer 査読有り

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

The Journal of Physical Chemistry Letters   15 巻 ( 5 ) 頁： 1469 - 1476   2024年1月

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

DOI： 10.1021/acs.jpclett.3c03337

Effect of Internal Substituents on the Properties of Dibenzo[<i>g</i>,<i>p</i>]chrysene 査読有り

Yoshihiro Takeo, Junichiro Hirano, Norihito Fukui, Hiroshi Shinokubo

Organic Letters     2023年12月

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

DOI： 10.1021/acs.orglett.3c03428

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

Junichiro Hirano, Hiroshi Shinokubo, Norihito Fukui

Chemistry Letters   53 巻 ( 1 )   2023年12月

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

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

Intrinsic Photostability in Dithiolonaphthalimide Achieved by Disulfide Bond-Induced Excited-State Quenching 査読有り

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

The Journal of Physical Chemistry Letters     頁： 8485 - 8492   2023年9月

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

DOI： 10.1021/acs.jpclett.3c02260

Near‐Infrared‐Responsive Hydrocarbons Designed by π‐Extension of Indeno[1,2,3,4‐pgra]perylene at the 1,2,12‐Positions 査読有り

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

Chemistry – A European Journal     2023年1月

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

DOI： 10.1002/chem.202300249

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

Mai Odajima, Norihito Fukui, Hiroshi Shinokubo

Organic Letters   25 巻 ( 1 ) 頁： 282 - 287   2023年1月

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

DOI： 10.1021/acs.orglett.2c04173

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

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

Chemical Science   14 巻 ( 3 ) 頁： 635 - 642   2023年

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

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

Yoshihiro Takeo, Junichiro Hirano, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo

Organic Chemistry Frontiers   10 巻 ( 23 ) 頁： 5895 - 5901   2023年

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

In this study, we compare a bowl-shaped aromatic hydrocarbon with internal methoxy groups to related derivatives with hydrogen, methyl, and anisyl groups, evaluating their electron-accepting properties, electronic absorption spectra, and fullerene-binding behavior.

DOI： 10.1039/d3qo01661g

Gram‐Scale Diversity‐Oriented Synthesis of Dinaphthothiepine Bisimides as Soluble Precursors for Perylene Bisimides 査読有り

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

European Journal of Organic Chemistry   2022 巻 ( 31 )   2022年8月

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

DOI： 10.1002/ejoc.202200770

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejoc.202200770

Synthesis of Dibenzo[<i>h</i>,<i>t</i>]rubicene through Its Internally Dimethoxy-substituted Precursor 査読有り

Masaki Kato, Norihito Fukui, Hiroshi Shinokubo

Chemistry Letters   51 巻 ( 3 ) 頁： 288 - 291   2022年3月

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

DOI： 10.1246/cl.210754

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

Masaki Kato, Norihito Fukui, Hiroshi Shinokubo

Chemistry – A European Journal   28 巻 ( 2 )   2022年1月

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

DOI： 10.1002/chem.202103647

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

Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer 査読有り

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

Physical Chemistry Chemical Physics   24 巻 ( 22 ) 頁： 14007 - 14015   2022年

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

The model molecule, bis-ANI (consisting of two naphthalimide moieties) was studied to better understand the process of charge separation. It is found that the central amino linker facilitates the formation of a charge separation state in bis-ANI.

DOI： 10.1039/d2cp00295g

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

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

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

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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

Web of Science

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

Mai Odajima, Keita Tajima, Norihito Fukui, Hiroshi Shinokubo

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION     2021年6月

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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

Web of Science

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

Yuki Tanaka, Keita Tajima, Norihito Fukui, Hiroshi Shinokubo

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

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

V-shaped pi-systems are attractive research targets in organic chemistry and materials science. Our group has recently demonstrated that the conceptual insertion of a heteroatom into a perylene bisimide (PBI) core is an effective guideline for the design of non-planar PBI derivatives. Here we report the synthesis and properties of dinaphtho[1,8-bc:1 ',8 '-fg][1,5]dithiocine bisimide (DNDTBI), which represents a doubly sulfur-inserted PBI derivative. The X-ray diffraction analysis revealed that DNDTBI adopted a V-shaped structure with a dihedral angle of 67 degrees. DNDTBI exhibited higher electron-donating ability than singly sulfur-inserted PBI derivative owing to the antibonding interaction between the two neighboring sulfur atoms. The inversion barrier of the flipping motion of DNDTBI was ca. 30 kcal mol(-1), indicating the rigid nature of the V-shaped structure.

DOI： 10.1002/ajoc.202000722

Web of Science

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

Yuki Tanaka, Norihito Fukui, Hiroshi Shinokubo

NATURE COMMUNICATIONS   11 巻 ( 1 )   2020年8月

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

Carbon and hydrogen are fundamental components of organic molecules and a fascinating plethora of functions can be generated using these two elements. Yet, realizing attractive electronic structures only by using carbon and hydrogen remains challenging. Herein, we report the synthesis and properties of the C-70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption (up to ca. 1300nm), even though this molecule consists of only 34 carbon and 14 hydrogen atoms. A remarkably small highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap is confirmed by electrochemical measurement and theoretical calculations. Furthermore, as-indacenoterrylene is stable despite the absence of peripheral substituents, which contrasts with the cases of other NIR-absorbing hydrocarbons such as diradicaloids and antiaromatic molecules. The results of this study thus offer fundamental insights into the design of hydrocarbons with a small band gap. The synthesis of hydrocarbons with attractive electronic structures remains challenging. Here, the authors describe the synthesis and properties of the C70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption.

DOI： 10.1038/s41467-020-17684-6

Web of Science

その他リンク： http://www.nature.com/articles/s41467-020-17684-6

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

Hayakawa, S., Matsuo, K., Yamada, H., Fukui, N., Shinokubo, H.

Journal of the American Chemical Society   142 巻 ( 27 ) 頁： 11663 - 11668   2020年7月

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

DOI： 10.1021/jacs.0c04096

Scopus

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

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

Journal of the American Chemical Society     2019年12月

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

DOI： 10.1021/jacs.9b09556

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

Keita Tajima, Norihito Fukui, Hiroshi Shinokubo

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

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

We have prepared four 4-aminonaphthalene monoimide derivatives and examined the aggregation-induced emission (AIE) properties. A nitrogen-bridged dimer is AIE-active and exhibits bright green emission with a high quantum yield in the solid state. The X-ray diffraction analysis suggests that key to the bright luminescence is the favorable crystal packing dominated by CH/p interaction. The late-stage cyanation of the dimer tuned its AIE color from green to orange.

DOI： 10.1021/acs.orglett.9b03699

Web of Science

Singly and Doubly Sulfone-Inserted Porphyrin Arch-Tape Dimers 査読有り

Fukui Norihito, Osuka Atsuhiro

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   91 巻 ( 7 ) 頁： 1131 - 1137   2018年7月

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20180103

Web of Science

Scopus

Singly and Doubly 1,2-Phenylene-Inserted Porphyrin Arch-Tape Dimers: Synthesis and Highly Contorted Structures 査読有り

Norihito Fukui, Atsuhiro Osuka

Angewandte Chemie - International Edition   57 巻 ( 21 ) 頁： 6304 - 6308   2018年5月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Singly and doubly 1,2-phenylene-inserted NiII porphyrin arch-tape dimers 3 and 9 were synthesized from the corresponding β-to-β 1,2-phenylene-bridged NiII porphyrin dimers 5 and 11 via Ni0-mediated reductive cyclization and DDQ/Sc(OTf)3-promoted oxidative cyclization as key steps, respectively. Owing to the fused eight-membered ring(s), 3 showed a more contorted structure than those of previously reported arch-tape dimers 2 a and 2 b possessing a fused seven-membered ring. Furthermore, 9 displayed much larger molecular contortion. As the molecular contortion increases, the Q band of the absorption spectrum becomes more red-shifted and the electrochemcial HOMO–LUMO gap becomes smaller, reaching at 1294 nm and 0.77 eV in 9, respectively. The effect of molecular contortion on the electronic properties was studied by means of DFT calculations.

DOI： 10.1002/anie.201802494

Web of Science

Scopus

Embedding heteroatoms: an effective approach to create porphyrin-based functional materials 査読有り

Norihito Fukui, Keisuke Fujimoto, Hideki Yorimitsu, Atsuhiro Osuka

DALTON TRANSACTIONS   46 巻 ( 39 ) 頁： 13322 - 13341   2017年10月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Incorporation of planarized heteroatom(s) onto the porphyrin periphery is an effective approach to create porphyrin-based functional materials. In the last three decades, such an "embedding heteroatom" strategy has been actively explored in order to realize attractive electronic, optical, and electrochemical properties. This review aims to cover a variety of synthetic methodologies that have been developed for the construction of heteroatom-embedded porphyrins. Moreover, we also summarize their structure-property relationships as well as possible applications in various research fields including artificial photosynthesis, molecular engineering, organic electronics, and bioimaging.

DOI： 10.1039/c7dt02815f

Web of Science

Porphyrin Arch-Tapes: Synthesis, Contorted Structures, and Full Conjugation 査読有り

Norihito Fukui, Taeyeon Kim, Dongho Kim, Atsuhiro Osuka

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   139 巻 ( 26 ) 頁： 9075 - 9088   2017年7月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Porphyrin tapes possessing meso-meso beta-beta beta-beta triple direct linkages have been targets of extensive studies because of their fully conjugated characteristic pi-electronic networks. In this paper, we report porphyrin arch tapes that bear additional carbonyl group(s) or methylene group(s) inserted between one of the beta-beta linkage(s) of the porphyrin tapes. The carbonyl-inserted porphyrin arch-tapes were efficiently synthesized by double fusion reactions of beta-to-beta carbonyl-bridged porphyrin oligomers with DDQ and Sc(OTf)(3), and were converted to the methylene-bridged porphyrin arch-tapes via Luche reduction with NaBH4 and CeCl3 followed by ionic hydrogenation with HBF4 center dot OEt2 and BH3 center dot NEt3. While the conventional porphyrin tapes display rigid and planar structures and low solubilities, these porphyrin arch-tapes show remarkably contorted structures, flexible conformations, and improved solubilities because of the presence of the incorporated seven-membered ring(s). Interestingly, the methylene inserted arch-tapes exhibited conjugative electronic interactions that were comparable to those of porphyrin tapes probably owing to through-space interaction in the contorted conformations. The carbonyl-inserted arch-tapes displayed distinctly larger conjugative interactions owing to an active involvement of the carbonyl group(s) in the electronic conjugation. A similar trend was observed in the nonlinear optical properties, as evidenced by their two-photon absorption cross sections. Furthermore, as a benefit of the contorted structures, these porphyrin arch-tapes can catch C-60 fullerene effectively. Naturally, the electron-rich methylene-bridged arch-tapes exhibited larger association constants than the electron-deficient carbonyl-bridged arch-tapes. Among these arch-tapes, a methylene-bridged syn-Ni(II) porphyrin trimer recorded the largest association constant of (1.5 +/- 0.4) X 10(7) M-1 in toluene at 25 degrees C.

DOI： 10.1021/jacs.7b05332

Web of Science

meso-to-meso Pt-II-bridged Ni-II-porphyrin dimers 査読有り

Norihito Fukui, Hua-Wei Jiang, Atsuhiro Osuka

ORGANIC CHEMISTRY FRONTIERS   4 巻 ( 5 ) 頁： 767 - 772   2017年5月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The synthesis and characterization of meso-to-meso Pt-II-bridged Ni-II-porphyrin dimers 5-7 are reported herein. A boron-platinum exchange reaction of meso-pinacolatoborylporphyrin 8 with Pt(cod) Cl-2 afforded the cod-coordinated meso-to-meso Pt-II-linked cis-dimer 5, which was subsequently converted to the 1,3-bis(diphenylphosphino) propane (DPPP)-coordinated cis-dimer 6 and the PPh3-coordinated trans-dimer 7 upon treatment with DPPP and PPh3, respectively. On the other hand, a reaction of 5 with tri-tert-butylphosphine induced reductive elimination to give the meso-meso directly linked diporphyrin 9. Comparative studies of these Pt-II-bridged Ni-II-porphyrin dimers were conducted by UV/Vis absorption spectroscopy, electrochemical studies, and theoretical calculations. In the course of these studies, we found that cis-dimers 5 and 6 underwent an unprecedented reductive elimination to give the mesomeso linked dimer 9 upon chemical or electrochemical one-electron oxidation, while trans-dimer 7 was stable under such conditions.

DOI： 10.1039/c7qo00093f

Web of Science

Highly planar diarylamine-fused porphyrins and their remarkably stable radical cations 査読有り

Norihito Fukui, Wonhee Cha, Daiki Shimizu, Juwon Oh, Ko Furukawa, Hideki Yorimitsu, Dongho Kim, Atsuhiro Osuka

CHEMICAL SCIENCE   8 巻 ( 1 ) 頁： 189 - 199   2017年1月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Oxidative fusion reactions of meso-phenoxazino Ni(II) porphyrin were found to be temperature dependent, giving rise to either a doubly phenylene-fused product at room temperature or a singly phenoxazine-fused product at 70 degrees C. The latter was further oxidized to a doubly phenoxazine-fused Ni(II) porphyrin, which was subsequently converted to the corresponding free base porphyrin and Zn(II) porphyrin. Compared to previously reported diphenylamine-fused porphyrins that displayed a molecular twist, doubly phenoxazine-fused porphyrins exhibited distinctly different properties owing to their highly planar structures, such as larger fluorescence quantum yields, formation of an offset face-to-face dimer both in solution and the solid state, and the generation of a mixed-valence p-radical cation dimer upon electrochemical oxidation. One-electron oxidation of the phenoxazine-fused Ni(II) porphyrin with Magic Blue gave the corresponding radical cation, which was certainly stable and could be isolated by separation over a silica gel column but slowly chlorinated at the reactive beta-positions in the solid state. This finding led to us to examine beta, beta'-dichlorinated phenoxazine-fused and diphenylamine-fused Ni(II) porphyrins, which, upon treatment with Magic Blue, provided remarkably stable radical cations to an unprecedented level. It is actually possible to purify these radical cations by silica gel chromatography, and they can be stored for over 6 months without any sign of deterioration. Moreover, they exhibited no degradation even after the CH2Cl2 solution was washed with water. However, subtle structural differences (planar versus partly twisted) led to different crystal packing structures and solid-state magnetic properties.

DOI： 10.1039/c6sc02721k

Web of Science

Homochiral and Heterochiral Self‐Sorting Assemblies of Antiaromatic Ni(II) Norcorrole Dimers 査読有り

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

Chemistry – A European Journal   30 巻 ( 39 )   2024年5月

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

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

Changing aromatic properties through stacking: the face-to-face dimer of Ni(<scp>ii</scp>) bis(pentafluorophenyl)norcorrole 査読有り

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

Physical Chemistry Chemical Physics   26 巻 ( 20 ) 頁： 14777 - 14786   2024年5月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：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

Close Stacking of Antiaromatic Ni(II) Norcorrole Originating from a Four-Electron Multicentered Bonding Interaction 査読有り

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   146 巻 ( 13 ) 頁： 9311 - 9317   2024年3月

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

DOI： 10.1021/jacs.4c01142

A Triply Linked Porphyrin‐Norcorrole Hybrid with Singlet Diradical Character 査読有り

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

Angewandte Chemie International Edition     2024年2月

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

Abstract

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

DOI： 10.1002/anie.202401233

Supramolecular Assemblies of Closely Stacked Antiaromatic Ni(II) Norcorrole Dimers via Homochiral and Heterochiral Self-Sorting 査読有り

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

    2023年11月

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

Stacking between aromatic π-systems is fundamental to the design of supramolecular assemblies. Recently, π–π stacked antiaromatic π-systems have received considerable attention as some antiaromatic compounds can form closely stacked structures with substantial in-termolecular orbital interactions, resulting in the emergence of stacked-ring aromaticity. Here, we report three covalently linked norcor-role dimers that self-assemble to form supramolecular architectures. A 2,2’-linked norcorrole dimer with 3,5-di-tert-butylphenyl groups forms a face-to-face 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 macro-cyclic 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： 10.26434/chemrxiv-2023-87qjz

A Double Bond Between Two Molecules 査読有り

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

    2023年11月

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

π-Conjugated molecules with one electronic spin often form π-stacked dimers via molecular-orbital interactions between the two unpaired electrons. These interactions are recognized as intermolecular single bonds between two π-conjugated systems. This then raises the question if a double bond between two such molecules is possible. To answer this question, we have synthesized an antiaromatic Ni(II) bis(pentafluorophenyl)norcorrole. Its dimer adopts a face-to-face-stacked structure with an extremely short stacking distance of 2.97 Å. Importantly, an intermolecular double bond does indeed exist in this system and this bond involves four bonding electrons between the two molecules. The bonding electrons were experimentally observed via synchrotron X-ray diffraction analysis and corroborated by theoretical calculations. The intermolecular interaction of the molecular orbitals imparts the stacked dimer with an aromatic character that is distinctly different from that of its monomer.

DOI： 10.26434/chemrxiv-2023-2brcz

Inner-Bond Cleavage in Nanographenes: A Constructive Destruction Strategy for Facile Access to Molecules with Multiple Figure-Eight Structures 査読有り

Yuki Sakamoto, Junichiro Hirano, Emiko Nishimoto, Daisuke Owase, Ren Takayanagi, Keita Tajima, Takuya Omine, Fumitaka Ishiwari, Akinori Saeki, Jinseok Kim, Juwon Oh, Dongho Kim, Tomoyuki Ikai, Eiji Yashima, Hiroshi Shinokubo, Norihito Fukui

    2023年5月

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

The elegant architectures of nonplanar π-systems, such as fullerene and corannulene, exhibit distinctive functionalities that have played a significant role in advancing science and technology. The current approach to synthesizing nonplanar π-systems heavily relies on the stepwise formation of bonds between their constituent fragments, which is known as the bottom-up approach. The limited number of synthetic pathways to nonplanar π-systems inevitably results in impractical molecular frameworks. Herein, we demonstrate that a constructive destruction approach, based on the oxidative cleavage of internal double bonds of dibenzo[g,p]chrysene that immediately produces eightphenone: the first readily available figure-eight molecule. Eightphenone adopts a D2-symmetric structure with excellent configurational stability and is a highly efficient emitter of circularly polarized phosphorescence. The oxidative cleavage of internal double bonds is also applicable to larger nanographene molecules, resulting in unprecedented structures with multiple figure-eight units. This study introduces the concept of constructive destruction as an alternative to conventional bottom-up approaches, paving the way for the design of new materials.

DOI： 10.26434/chemrxiv-2023-f1djk-v2

Easily Switchable 18π‐, 19π‐, and 20π‐Conjugation of Diazaporphyrin Double‐Pincer Bispalladium Complexes 査読有り

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

Angewandte Chemie International Edition   62 巻 ( 12 )   2023年2月

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

DOI： 10.1002/anie.202300437

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

One-dimensional stacking array of 10,20-diphenyl-5,15-diazaporphyrin metal complexes 査読有り

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

Journal of Porphyrins and Phthalocyanines     頁： A - G   2023年1月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：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

Highly soluble Ni(II) dithienylnorcorrole 査読有り

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

Journal of Porphyrins and Phthalocyanines     頁： A - E   2022年11月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：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 査読有り

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     2022年10月

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

DOI： 10.1021/jacs.2c08795

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

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

Cell Reports Physical Science   3 巻 ( 9 ) 頁： 101045 - 101045   2022年9月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier {BV}  

DOI： 10.1016/j.xcrp.2022.101045

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

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

Chemistry Letters   51 巻 ( 3 ) 頁： 321 - 324   2022年3月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：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

Web of Science

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

Shusaku Ukai, Norihito Fukui, Takahisa Ikeue, Hiroshi Shinokubo

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

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

DOI： 10.1246/cl.210715

A Supramolecular Polymer Constituted of Antiaromatic Ni II Norcorroles 査読有り

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

Angewandte Chemie International Edition   61 巻 ( 6 )   2022年2月

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

DOI： 10.1002/anie.202114230

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202114230

<scp>d</scp>-Mannose-appended 5,15-diazaporphyrin for photodynamic therapy 査読有り

Lamiaa M. A. Ali, Kazuya Miyagawa, Norihito Fukui, M{\'{e } }lanie Onofre, Khaled El Cheikh, Alain Mor{\`{e } }re, S{\'{e } }bastien Cl{\'{e } }ment, Magali Gary-Bobo, S{\'{e } }bastien Richeter, Hiroshi Shinokubo

Organic &amp; Biomolecular Chemistry     2022年

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

5,15-Diazaporphyrin appended with d-mannose moieties was prepared through Suzuki–Miyaura cross-coupling reaction and S_N2 alkylation.

DOI： 10.1039/d2ob01410f

Antiaromatic 1,5‐Diaza‐ <i>s</i> ‐indacenes 査読有り

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

Angewandte Chemie International Edition   60 巻 ( 38 ) 頁： 20765 - 20770   2021年9月

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

DOI： 10.1002/anie.202109003

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202109003

Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes 査読有り

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

Journal of the American Chemical Society   143 巻 ( 28 ) 頁： 10676 - 10685   2021年7月

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

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

DOI： 10.1021/jacs.1c04348

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

Kazuya Miyagawa, Ichiro Hisaki, Norihito Fukui, Hiroshi Shinokubo

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

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

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

[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

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Replacement of the meso methine carbon atoms of porphyrins with heteroatoms is a powerful strategy for tuning their optical and electronic properties. In particular, 5-oxaporphyrin is an attractive target due to its importance as an intermediate in heme catabolism. In this work, we describe the synthesis and properties of a free-base 5-oxaporphyrinium cation, which was prepared by the ring-closure of a bilindione with trifluoromethanesulfonic anhydride. This free-base 5-oxaporphyrinium cation exhibits dual fluorescence originating from its unique NH tautomerism. In contrast to normal porphyrins, the cis form of the 5-oxaporphyrinium cation is more stable than the trans form due to the effective delocalization of its positive charge. We thus demonstrate here that meso-modified heteroporphyrins enable the manipulation of NH tautomerism in porphyrinic macrocycles.

DOI： 10.1002/anie.202013542

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

meso-Dimethylnorcorrole Ni-II complex exhibited enough stability under ambient conditions despite the distinct antiaromaticity. The small methyl substituents realized a dense and long-range p-stacking in its solid state, which resulted in the superior electron-transporting ability to previously reported Ni-II norcorroles.

DOI： 10.1039/d0dt03143g

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Norcorrole is a ring-contracted porphyrinoid, exhibiting distinct antiaromaticity. Herein, we report the reactions of meso-dimesitylnorcorrole Ni(II) complex with two types of carbenes: dichlorocarbene and an N-heterocyclic carbene (NHC). The reaction with in-situ-generated dichlorocarbene resulted in the double insertion of two chloromethine units to provide a mixture of 5,15-dichloroporphyrin and chlorinated isopyricorroles. The nucleophilic NHC attacked the 3-position of the norcorrole core and the subsequent proton transfer furnished a nonconjugated macrocycle incorporating a diazafulvene segment.

DOI： 10.1021/acs.orglett.0c01402

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The synthesis and properties of a 2-to-2 ' 18-to-18 ' doubly linked Ni(ii) norcorrole dimer are described. It adopts a highly planar structure, resulting in effective electronic interactions between the constituent norcorrole units. Nevertheless, each norcorrole unit exhibits substantial antiaromaticity, which stands in sharp contrast to stacked norcorrole dimers.

DOI： 10.1039/d0cc02543g

Web of Science

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

Yamashita D, Omori H, Fukui N, Shinokubo H

Journal of Porphyrins and Phthalocyanines   24 巻 ( 1-3 ) 頁： 84 - 89   2020年1月

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1142/S108842461950069X

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Scopus

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

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

CHEMISTRY-A EUROPEAN JOURNAL   25 巻 ( 68 ) 頁： 15580 - 15585   2019年12月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the Ni-II center was significantly higher than those of conventional porphyrin Ni-II complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin Ni-II complex revealed the presence of weak ferromagnetic interactions.

DOI： 10.1002/chem.201903639

Web of Science

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

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

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The synthesis of antiaromatic Ni-II-norcorroles having primary, secondary, and tertiary alkyl groups at the reactive meso-positions was attempted. Reductive coupling of a Ni-II-dipyrrin precursor provided Ni-II-meso-dihexylnorcorrole, which underwent substantial degradation on silica gel. Introduction of tert-butyl groups was unsuccessful due to the difficult preparation of the corresponding dipyrrin precursor. Meanwhile, Ni-II-norcorroles with isopropyl and cyclohexyl groups were isolated as stable molecules under ambient conditions. Furthermore, we found that oxidation of Ni-II-meso-dialkylnorcorroles with hydrogen peroxide in the presence of sodium carbonate gave Ni-II-5-oxaporphyrins(2.0.1.0). In contrast, oxidation of Ni-II-meso-dimesitylnorcorrole under the same reaction conditions gave 10-oxaporphyrin(1.1.1.0). The contrasting reactivity can be attributed to the steric congestion around the meso-positions.

DOI： 10.1002/chem.201901292

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Scopus

Synthesis of Hydroxyisooxophlorins by Oxidative Degradation of meso-Hydroxyporphyrins 査読有り

Asahi Takiguchi, Norihito Fukui, Hiroshi Shinokubo

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

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Hydroxyisooxophlorin is an oxidatively degraded porphyrin that contains one carbonyl carbon, one hydroxymethylene group, and two sp(2)-methine groups at its meso positions. Here we report that oxidation of a free-base meso-hydroxyporphyrin with [bis(trifluoroacetoxy)iodo]benzene in the presence of H2O afforded two regioisomers of hydroxyisooxophlorins, 10-hydroxy-10-iso-5-oxophlorin and 15-hydroxy-15-iso-5-oxophlorin, as major and minor products, respectively. We also examined the reaction mechanism, acid-mediated isomerization, metal complexation behavior, and physical properties of these molecules.

DOI： 10.1021/acs.orglett.9b01066

Web of Science

Scopus

Organic Transformations by the Hydrosilane-Alkoxide System 査読有り

Fukui Norihito

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   77 巻 ( 5 ) 頁： 512 - 513   2019年5月

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.5059/yukigoseikyokaishi.77.512

Web of Science

Scopus

Macroscopically Anisotropic Structures Produced by Light-induced Solvothermal Assembly of Porphyrin Dimers 査読有り

Yamamoto Yasuyuki, Nishimura Yushi, Tokonami Shiho, Fukui Norihito, Tanaka Takayuki, Osuka Atsuhiro, Yorimitsu Hideki, Iida Takuya

SCIENTIFIC REPORTS   8 巻   2018年7月

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41598-018-28311-2

Web of Science

Diarylamine-Fused Subporphyrins: Proof of Twisted Intramolecular Charge Transfer (TICT) Mechanism 査読有り

Koki Kise, Yongseok Hong, Norihito Fukui, Daiki Shimizu, Dongho Kim, Atsuhiro Osuka

Chemistry - A European Journal   24 巻 ( 33 ) 頁： 8306 - 8310   2018年6月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Diarylamine-fused subporphyrins 1 a and 1 b were synthesized from β,β-diiodo-meso-chloro subporphyrin 2 through a one-pot procedure involving nucleophilic aromatic substitution and SRN1-type intramolecular fusion reaction as the first example of meso-nitrogen-embedded subporphyrin. While non-fused counterparts 3 b and 4 b display effective fluorescence quenching due to twisted intramolecular charge transfer (TICT) in CH2Cl2 at room temperature, 1 b emits fluorescence with ΦF=0.18 under the same conditions, because conformational twisting is not allowed due to the fused structure. In addition, the oxidative titration with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave cation radical 7 for 1 a and cation radical and dication for 1 b. Actually, cation radical 7 was isolated through separation over silica gel column but was found to slowly decompose in concentrated solutions.

DOI： 10.1002/chem.201801576

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Metalation Control of Open-Shell Character in meso-meso Linked Porphyrin meso-Oxy Radical Dimers 査読有り

Yuta Jun-i, Norihito Fukui, Ko Furukawa, Atsuhiro Osuka

Chemistry - A European Journal   24 巻 ( 7 ) 頁： 1528 - 1532   2018年2月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Control of open-shell character of meso-meso linked porphyrin meso-oxy radical dimers has been demonstrated by core metalation. Namely, NiII-porphyrin dimer 6Ni exhibits a clear 1H NMR spectrum and a distorted but rather coplanar quinonoidal structure consisting of two ruffled porphyrin rings, in accordance with the previous report. Freebase dimer 6H2 shows a similar quinonoidal structure in the solid state but displays slightly broader and temperature-dependent 1H NMR spectra, indicating a partial diradical character in solution that increases at high temperature. In sharp contrast, bis-imidazole-coordinated ZnII-porphyrin dimer 6ZnIm2 exhibits a perpendicular structure consisting of two planar ZnII-porphyrins and has been characterized as a distinct open-shell diradical on the basis of its non-observable 1H NMR signals, a clear ESR signal, and a characteristic absorption spectrum reaching about 1700 nm. Despite the distinct diradical character, 6ZnIm2 is an extremely stable molecule.

DOI： 10.1002/chem.201705769

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Scopus

A meso-meso - - Triply Linked Subporphyrin Dimer 査読有り

Yasuhiro Okuda, Norihito Fukui, Jinseok Kim, Taeyeon Kim, Hua-Wei Jiang, Graeme Copley, Masaaki Kitano, Dongho Kim, Atsuhiro Osuka

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   56 巻 ( 40 ) 頁： 12317 - 12321   2017年9月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

A meso-meso - - triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of -to- doubly Pt-II-bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942nm and a small electrochemical HOMO-LUMO gap (1.35eV), indicating an effectively conjugated -electronic network.

DOI： 10.1002/anie.201707123

Web of Science

Diphenylphosphine-Oxide-Fused and Diphenylphosphine-Fused Porphyrins: Synthesis, Tunable Electronic Properties, and Formation of Cofacial Dimers 査読有り

Keisuke Fujimoto, Yuko Kasuga, Norihito Fukui, Atsuhiro Osuka

CHEMISTRY-A EUROPEAN JOURNAL   23 巻 ( 28 ) 頁： 6741 - 6745   2017年5月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Diphenylphosphine-oxide-fused Ni-II porphyrin 8 was synthesized from 3,5,7-trichloroporphyrin 5 via a reaction sequence of nucleophilic aromatic substitution with lithium diphenylphosphide, oxidation with H2O2, and palladium-catalyzed intramolecular cyclization. Reduction of 8 with HSiCl3 gave diphenylphosphine-fused Ni-II porphyrin 9. The embedded P=O and P moieties serve as a strong electron-accepting and electron-donating group to perturb the optical and electrochemical properties of the Ni-II porphyrin. Ni-II porphyrin 9 is diamagnetic with a low-spin Ni-II center in solution but becomes paramagnetic with a five-coordinated Ni-II center with high-spin (S=1) state in the solid state. Diphenylphosphine-oxide-fused Zn-II porphyrin 10 was also synthesized and shown to form a face-to-face dimer with mutual O-Zn bonds in the crystal and in nonpolar and moderately polar solvents. The dimerization of 10 in CDCl3 has been revealed to be an entropy-driven process with a large entropy gain (S-D=207JK(-1)mol(-1)).

DOI： 10.1002/chem.201700909

Web of Science

Aromatic Metamorphosis of Dibenzofurans into Triphenylenes Starting with Nickel-Catalyzed Ring-Opening C-O Arylation 査読有り

Yuto Kurata, Shinya Otsuka, Norihito Fukui, Keisuke Nogi, Hideki Yorimitsu, Atsuhiro Osuka

ORGANIC LETTERS   19 巻 ( 6 ) 頁： 1274 - 1277   2017年3月

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

A new class of aromatic metamorphosis has been developed in which dibenzofurans were converted into triphenylenes. This transformation is composed of three successive operations: (1) nickel-catalyzed ring-opening C-O bond arylation with arylmagnesium bromides, (2) trifluoromethanesulfonylation (triflation) of the resulting hydroxy moiety with Tf2O, and (3) palladium-catalyzed or photoinduced ring closure. In the last ring-closing step, the photoinduced process has proven to be more productive than the palladium-catalyzed one. By employing pi-extended dinaphthofuran as the substrate, dorsally benzo-fused [5]helicene was obtained in a satisfactory yield.

DOI： 10.1021/acs.orglett.6b03861

Web of Science