研究者詳細 - 忍久保　洋

Highly soluble Ni(II) dithienylnorcorrole 招待有り査読有り国際共著国際誌

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

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES 頁： A - E 2022年11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 Porphyrins and Phthalocyanines

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 査読有り国際共著国際誌

Liu Si-Yu, Kishida Natsuki, Kim Jinseok, Fukui Norihito, Haruki Rie, Niwa Yasuhiro, Kumai Reiji, Kim Dongho, Yoshizawa Michito, Shinokubo Hiroshi

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145 巻 ( 4 ) 頁： 2135 - 2141 2022年10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

Stacked-ring aromaticity arising from the close stacking of antiaromatic π-systems has recently received considerable attention. Here, we realize stacked-ring aromaticity via a rational supramolecular approach. A nanocapsule composed of bent polyaromatic amphiphiles was employed to encapsulate several antiaromatic norcorrole Ni(II) complexes (NCs) in water. The resulting micellar capsules display high stability toward heating and concentration change. The encapsulation resulted in the appearance of a broad absorption band in the near-infrared region, which is characteristic of norcorroles with close face-to-face stacking. Importantly, a meso-isopropyl NC, which does not exhibit π-stacking even in a concentrated solution or the crystalline phase, adopted π-stacking with stacked-ring aromaticity in the supramolecular micellar capsule.

DOI： 10.1021/jacs.2c08795

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

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

CELL REPORTS PHYSICAL SCIENCE 3 巻 ( 9 ) 頁： 101045 - 101045 2022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：Cell Reports Physical Science

A bowl-shaped π-conjugated molecule typically undergoes bowl-inversion motion via a planarized transition state (TS), the highest-energy state along the reaction coordinate between two minimum bowl structures. Isolation of such planarized state has been challenging. Here, we report that a platinum(II) complex of antiaromatic porphyrin, norcorrole, adopts bowl-shaped conformation in solution but can become planar in solid. In the crystalline state, the norcorrole Pt(II) complex forms triple-decker stacking structures, in which the planarized norcorrole is stabilized and sandwiched between two bowl-shaped norcorroles. The planar conformation corresponds to the TS structure in the dynamic bowl-to-bowl inversion motion of the bowl-shaped molecule. Detailed theoretical studies have revealed that the intrinsically unstable planar conformation is stabilized by the dispersion force among the substituents and enhanced Pt–Pt interactions created by the antiaromatic macrocyclic ligand.

DOI： 10.1016/j.xcrp.2022.101045

d-Mannose-appended 5,15-diazaporphyrin for photodynamic therapy 査読有り国際共著国際誌

Ali Lamiaa M. A., Miyagawa Kazuya, Fukui Norihito, Onofre Melanie, El Cheikh Khaled, Morere Alain, Clement Sebastien, Gary-Bobo Magali, Richeter Sebastien, Shinokubo Hiroshi

ORGANIC & BIOMOLECULAR CHEMISTRY 2022年8月

Gram-Scale Diversity-Oriented Synthesis of Dinaphthothiepine Bisimides as Soluble Precursors for Perylene Bisimides 査読有り国際誌

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

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2022 巻 ( 31 ) 2022年8月

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

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

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

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

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

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

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

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