研究者詳細 - 忍久保　洋

論文 - 忍久保　洋

分割表示 403 件中 41 - 60 件目／全件表示 >>

Stepwise N-Methylation of Ruthenium and Cobalt 5,15-Diazaporphyrins: Post-Functionalization of Porphyrinoid Catalysts 査読有り国際誌

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

CHEMISTRY-AN ASIAN JOURNAL 17 巻 ( 14 ) 頁： e202200305 2022年7月

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：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

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Protonation-Induced Antiaromaticity in Octaaza[8]circulenes: Cyclooctatetraene Scaffolds Constrained with Four Amidine Moieties 査読有り国際共著国際誌

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

CHEMISTRY-AN ASIAN JOURNAL 17 巻 ( 12 ) 頁： e202200244 2022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：Chemistry - An Asian Journal

The switching of cyclic π-conjugation pathways using external stimuli is an attractive research topic in the field of organic chemistry. Here, we synthesized C4h-symmetric octaaza[8]circulenes with four peripherally arranged amidine moieties that exhibit enhanced antiaromaticity upon protonation. Titration experiments with methanesulfonic acid revealed the formation of the tetraprotonated forms of the octaaza[8]circulenes in solution. Single-crystal X-ray diffraction analyses and theoretical calculations indicated that the contribution of the 8π antiaromatic character of the octaaza[8]circulenes is enhanced by the delocalization of charge through the protonation of the pyridine rings.

DOI： 10.1002/asia.202200244

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Symmetry-breaking charge separation in a nitrogen-bridged naphthalene monoimide dimer 査読有り国際共著国際誌

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

PHYSICAL CHEMISTRY CHEMICAL PHYSICS 24 巻 ( 22 ) 頁： 14007 - 14015 2022年6月

Synthesis and Tautomerization of 5-Azaporphyrinium Cations 査読有り国際誌

Takiguchi Asahi, Shinokubo Hiroshi

CHEMISTRY LETTERS 51 巻 ( 6 ) 頁： 590 - 593 2022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：公益社団法人日本化学会

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 ¢-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

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CiNii Research

5-Thiaporphyrinium cation: effect of sulphur incorporation on excited state dynamics 査読有り国際共著国際誌

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

CHEMICAL COMMUNICATIONS 58 巻 ( 40 ) 頁： 5956 - 5959 2022年5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 Communications

We synthesised thionium-ion embedded aromatic porphyrinoids: a free-base 5-thiaporphyrinium cation and its zinc complex. The sulphur atom effectively participates in the macrocyclic π-conjugation. Fluorescence quantum yields of thiaporphyrinium cations were lower than 1% unlike oxaporphyrinium cations. Detailed photophysical analysis and DFT calculations clarified the vibrational mode regarding the out-of-plane motion of the sulphur atom induced ultrafast quenching of the excited state in comparison to the corresponding oxaporphyrinium cations.

DOI： 10.1039/d2cc00522k

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Diverse Crystal Structures of Ion Pairs Consisting of Oxaporphyrinium Cations and Pentacyanocyclopentadienide 査読有り

Asahi Takiguchi, Hiroki Tanaka, Hiromitsu Maeda, Hiroshi Shinokubo

Bulletin of the Chemical Society of Japan 95 巻 ( 5 ) 頁： 796 - 801 2022年3月

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

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

CHEMISTRY LETTERS 51 巻 ( 3 ) 頁： 321 - 324 2022年3月

Synthesis of Dibenzo[h,t]rubicene through Its Internally Dimethoxy-substituted Precursor 査読有り国際誌

Kato Masaki, Fukui Norihito, Shinokubo Hiroshi

CHEMISTRY LETTERS 51 巻 ( 3 ) 頁： 288 - 291 2022年3月

A Heme-Acquisition Protein Reconstructed with a Cobalt 5-Oxaporphyrinium Cation and Its Growth-Inhibition Activity Toward Multidrug-Resistant Pseudomonas aeruginosa 査読有り国際誌

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

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61 巻 ( 7 ) 頁： e202112456 2022年2月

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

Ukai Shusaku, Fukui Norihito, Ikeue Takahisa, Shinokubo Hiroshi

Chemistry Letters 51 巻 ( 2 ) 頁： 182 - 184 2022年2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：The Chemical Society of Japan

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

DOI： 10.1246/cl.210715

A Supramolecular Polymer Constituted of Antiaromatic Ni(II) Norcorroles 査読有り国際誌

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

Angewandte Chemie International Edition 61 巻頁： e202114230 2022年2月

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

Kato, M; Fukui, N; Shinokubo, H

CHEMISTRY-A EUROPEAN JOURNAL 28 巻 ( 2 ) 頁： e202103647 2022年1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 indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C24H12 that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.

DOI： 10.1002/chem.202103647

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

Dual-Ion NiNc Battery: A Sustainable Revolution for Sodium Organic Batteries 査読有り国際誌

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

BATTERIES & SUPERCAPS 4 巻 ( 10 ) 頁： 1605 - 1610 2021年10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：Batteries and Supercaps

Dual-ion mobilities of Na organic batteries are investigated with in-situ XRD analysis and computational estimation considering molecular alignments in the solid state, signifying the interactive variations of ionic-pairs of an ionic liquid electrolyte and an antiaromatic molecule, nickel(II) norcorrole (NiNc). An appropriate cavity sphere in three-dimensional molecular alignments dispensed mobilities of dual-ion in an ionic liquid, resulting in high battery capacities, supplemented with the comparison of Mes-NiNc and Ph-NiNc molecular alignments. In-situ XRD experiment, computation, and simulation perspectives afforded prospective insertion and desertion behaviors of cations and anions.

DOI： 10.1002/batt.202100193

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Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C-H fluorination 査読有り国際誌

Mori Shiho, Nishimura Tsubasa, Shinokubo Hiroshi, Miyake Yoshihiro

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 25 巻 ( 10N12 ) 頁： 991 - 996 2021年10月

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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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

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論文 - 忍久保 洋

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論文 - 忍久保　洋