研究者詳細 - 忍久保　洋

論文 - 忍久保　洋

分割表示 409 件中 61 - 80 件目／全件表示 >>

Antiaromatic 1,5-Diaza-s-indacenes 査読有り国際共著国際誌

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 38 ) 頁： 20765 - 20770 2021年9月

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

s-Indacene is a classical non-alternant hydrocarbon that contains 12 π-electrons in a cyclic π-conjugation system. Herein, we report its nitrogen-doped analogue, 1,5-diaza-s-indacene. 1,5-Diaza-s-indacenes were readily prepared from commercially available 2,5-dichlorobenzene-1,4-diamine through a two-step transformation consisting of a palladium-catalyzed Larock cyclization with diaryl acetylenes followed by hydrogen abstraction. The thus obtained 1,5-diaza-s-indacenes exhibited distinct antiaromaticity, as manifested in clear bond-length alternation, a forbidden HOMO–LUMO transition, and a paratropic ring current. As compared to the parent s-indacene, the 1,5-diaza-s-indacenes showed higher electron-accepting ability owing to the presence of imine-type nitrogen atoms. The 1,5-diaza-s-indacene core is effectively conjugated with the peripheral aryl groups, which enables fine-tuning of the absorption spectra and redox properties. The two possible localized forms of 1,5-diaza-s-indacene were compared in terms of their energetic aspects.

DOI： 10.1002/anie.202109003

Synthesis of Tetrasilatetrathia[8]circulenes through C-I and C-H Silylation 招待有り査読有り国際誌

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

SYNTHESIS-STUTTGART 53 巻 ( 17 ) 頁： 2995 - 3000 2021年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Georg Thieme Verlag KG

<jats:title>Abstract</jats:title><jats:p>We have succeeded in the synthesis of various tetrasilatetrathia[8]circulenes with alkyl and aryl groups on the silicon atoms. We also disclosed the effect of phosphine ligands on palladium-catalyzed silylation of tetraiodotetrathienylene and rhodium-catalyzed intramolecular silylation of tetrasilyltetrathienylenes. Experimental and theoretical analysis revealed the effect of the substituents on the silicon atoms on their electronic property.</jats:p>

DOI： 10.1055/a-1437-9917

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Scopus

Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes 査読有り国際共著国際誌

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 143 巻 ( 28 ) 頁： 10676 - 10685 2021年7月

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

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

DOI： 10.1021/jacs.1c04348

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

Odajima Mai, Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 29 ) 頁： 15838 - 15843 2021年7月

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

The synthesis and properties of dinaphthotropone bisimide (DNTrBI) and dinaphthocycloheptatriene bisimide (DNCHepBI) are described. Their molecular design is conceptually based on the insertion of a carbon atom into a perylene bisimide (PBI) core. These molecules adopt non-planar structures due to the presence of a seven-membered ring. The PBI derivative into which a carbonyl group was inserted (DNTrBI) immediately underwent nonradiative decay and/or intersystem crossing in its excited state. The PBI derivative into which a methylene group was inserted (DNCHepBI) was susceptible to deprotonation on account of the two electron-withdrawing naphthalene monoimide units. Subsequent aerobic oxidation resulted in the formation of a C−C bond at the central methylene unit, thus affording a σ-dimer. The formation of this C−C bond is dynamically redox-active, i.e., electron injection into the σ-dimer almost quantitatively regenerated the deprotonated DNCHepBI.

DOI： 10.1002/anie.202104882

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

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

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

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

We report the synthesis and properties of acridino[2,1,9,8-klmna]acridine bisimide (AABI), a nitrogen-doped anthanthrene with two imide functionalities. AABI exhibits excellent electron affinity as evident by its low-lying LUMO level (−4.1 eV vs. vacuum). Single-electron reduction of one AABI derivative afforded the corresponding radical anion, which was stable under ambient conditions. Photoconductivity measurements suggest that the intrinsic electron mobility of an N-phenethyl AABI derivative obeys a band-transport model. Accordingly, an electron mobility of 0.90 cm2 V−1 s−1 was attained with the corresponding single-crystal organic field-effect transistor (OFET) device. The vacuum-deposited OFET device consisting of a polycrystalline sample exhibited high electron mobility of up to 0.27 cm2 V−1 s−1 even in air. This study demonstrates that dual incorporation of both imide substituents and imine-type nitrogen atoms is an effective strategy to create novel electron-deficient π-systems.

DOI： 10.1002/anie.202102708

Synthesis and Characterization of 16 pi Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen 査読有り国際誌

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 巻 ( 25 ) 頁： 13877 - 13881 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Angewandte Chemie - International Edition

We describe the two-electron reduction of N,N′-dimethyl-2,7-diazapyrenium dications (MDAP2+), which afforded the corresponding reduced form (MDAP0) as a highly electron-rich 16π antiaromatic system. A single-crystal X-ray diffraction analysis of MDAP0 revealed a distorted quinoidal structure with high bond-length alternation. The 1H NMR spectrum of MDAP0 exhibited a diagnostic proton signal (4.6 ppm) that is distinctly upfield shifted compared to that of aromatic diazapyrene (8.3 ppm). Theoretical calculations supported the existence of a paratropic ring current. These results indicate that MDAP0 exhibits antiaromatic character derived from its peripheral 16π-electron conjugation.

DOI： 10.1002/anie.202103667

Quadruply BN-Fused Tetrathia[8]circulenes with Flexible Frameworks: Synthesis, Structures and Properties 査読有り国際誌

Akahori Shuhei, Sasamori Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL 27 巻 ( 31 ) 頁： 8178 - 8184 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

Quadruply BN-fused tetrathia[8]circulenes were synthesized through four-fold electrophilic borylation. The single-crystal X-ray diffraction analysis revealed that the BN-fused tetrathia[8]circulene with peripheral phenyl groups exhibits crystal polymorphism, in which the circulene core adopts both planar and saddle conformations in the solid state. The experimental and theoretical studies revealed that the weaker aromaticity of azaborine compared with benzene renders the flexibility of the BN-fused tetrathia[8]circulenes.

DOI： 10.1002/chem.202100454

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

Iron hexamesityl-5,15-diazaporphyrin: synthesis, structure and catalytic use for direct oxidation of sp(3) C-H bonds 査読有り国際誌

Nishimura Tsubasa, Sakurai Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

DALTON TRANSACTIONS 50 巻 ( 18 ) 頁： 6343 - 6348 2021年5月

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

Iron hexamesityl-5,15-diazaporphyrin was synthesized through the cross-coupling reaction of tetrabromodiazaporphyrin. The use of chloroiron(iii) hexamesityl-5,15-diazaporphyrin as a catalyst for oxidation of cyclooctane showed high performance with a total TON up to 731. The introduction of bulky mesityl groups at β-positions prevented the catalyst deactivation via formation of a μ-oxo dimer.

DOI： 10.1039/d1dt00893e

Web of Science

Scopus

PubMed

Cationic Nickel(II) Pyridinophane Complexes: Synthesis, Structures and Catalytic Activities for C-H Oxidation 査読有り国際誌

Nishimura Tsubasa, Ando Yuki, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY LETTERS 50 巻 ( 5 ) 頁： 1049 - 1052 2021年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：公益社団法人日本化学会

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

DOI： 10.1246/cl.210074

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Scopus

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

Miyagawa Kazuya, Hisaki Ichiro, Fukui Norihito, Shinokubo Hiroshi

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

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

3,5-Ethenoporphyrin is a π-extended porphyrin containing a fused ethene unit between themeso- and β-positions, exhibiting unique contribution of macrocyclic antiaromaticity. We have recently reported that its analogue, etheno-fused diporphyrin, underwent thermal [2 + 2] cycloaddition to furnish X-shaped cyclobutane-linked tetraporphyrins. Here we demonstrate that the cyclobutane-ring formation is dynamically redox-active. Namely, the tetraporphyrin underwent two-step four-electron oxidation to afford two etheno-fused diporphyrin dications. The reduction of the resulting dication regenerated the cyclobutane-linked tetraporphyrin. The dication was sufficiently stable to allow its isolation under ambient conditions. The structure of the dication has been confirmed by1H NMR spectroscopy and X-ray diffraction analysis. Importantly, the simultaneous double C-C bond cleavage in the cyclopropane ring in the tetraporphyrin is exceptional among dynamic redox (dyrex) systems to achieve large structural changes, thus offering new insights for the design of novel redox-active functional organic materials for electrochromic dyes, organic batteries, and organic memories.

DOI： 10.1039/d1sc00438g

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

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

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

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

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

DOI： 10.1021/acs.orglett.1c00823

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

Akahori Shuhei, Sasamori Takahiro, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMISTRY-A EUROPEAN JOURNAL 27 巻頁： 5675 - 5682 2021年3月

Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation 査読有り

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

Organic Letters 23 巻 ( 6 ) 頁： 2099 - 2103 2021年3月

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

Tanaka Yuki, Tajima Keita, Fukui Norihito, Shinokubo Hiroshi

ASIAN JOURNAL OF ORGANIC CHEMISTRY 10 巻 ( 3 ) 頁： 541 - 544 2021年2月

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

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

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

Complexation of 2,7-diazapyrene with boron for structural and electronic tuning 査読有り

Nakazato Takumi, Shinokubo Hiroshi, Miyake Yoshihiro

CHEMICAL COMMUNICATIONS 57 巻 ( 3 ) 頁： 327 - 330 2021年1月

Dual-ion charge-discharge behaviors of Na-NiNc and NiNc-NiNc batteries 査読有り国際誌

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

MATERIALS ADVANCES 2 巻 ( 7 ) 頁： 2263 - 2266 2021年

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

Dual-ion sodium-organic secondary batteries were produced with anti-aromatic porphyrinoid, NiNc, as an active electrode material, which exhibited inherent charge-discharge behavior with high discharge capacity, high stability, and high Coulombic efficiency at high current density (132.6 mA h g-1 discharge capacity and 99.4% efficiency at the 100th cycle with 1 A g-1 of current density and 95.3 mA h g-1 discharge capacity and 99.3% efficiency at the 100th cycle with 2 A g-1 of current density).

DOI： 10.1039/D1MA00007A

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Hetero[8]circulenes: synthetic progress and intrinsic properties 招待有り査読有り

Miyake Yoshihiro, Shinokubo Hiroshi

CHEMICAL COMMUNICATIONS 56 巻 ( 100 ) 2020年12月

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

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

CHEMISTRY-AN ASIAN JOURNAL 15 巻 ( 22 ) 頁： 3873 - 3877 2020年11月

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

Longevial Jean-Francois, Miyagawa Kazuya, Shinokubo Hiroshi

DALTON TRANSACTIONS 49 巻 ( 42 ) 頁： 14786 - 14789 2020年11月

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