Papers - NAKAYA Manabu
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Spin-crossover cobalt(ii) complexes exhibiting temperature- and concentration-dependent optical changes in solution Invited Reviewed
Naoki Izumiyama, Shun Fujii, Kiichi Kato, Ryuya Tokunaga, Shinya Hayami, Manabu Nakaya
Dalton Transactions 53 ( 22 ) 9547 - 9553 2024.05
Authorship：Corresponding author Publishing type：Research paper (scientific journal)
This work investigated the spin states of the cobalt(ii) complexes [Co(L1)2](X)2 (1·X; L1 = 4′-(4-N,N′-diphenylaminophenyl)-2,2′:6′,2′′-terpyridine, X = PF6, BPh4) and [Co(L2)2](X)2 (2·X; L2 = 4′-(4-N,N′-dimethylaminophenyl)-2,2′:6′,2′′-terpyridine, X = PF6, BPh4) in the solid state and in solution. In the solid state, 1·PF6 and 2·PF6, both containing smaller PF6− counter anions, showed gradual spin-crossover. In contrast, 1·BPh4 and 2·BPh4 remained in the high-spin state over the temperature range of 5-400 K due to a lower degree of molecular cooperativity. Each of the cobalt(ii) complexes exhibited effects of temperature and concentration on their absorption spectra that were related to the spin states in various organic solvents. This work provides new insights into the spectroscopic properties resulting from the spin states of cobalt(ii) complexes in solution.
DOI： 10.1039/d4dt00433g
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pH-driven optical changes of platinum(II) complexes having carboxy-appended salophen ligands Reviewed
Shun Fujii, Hajime Yagi, Tomohiro Kawaguchi, Mitsuru Ishikawa, Naoki Izumiyama, Manabu Nakaya
Dalton Transactions 52 ( 29 ) 10206 - 10212 2023
Authorship：Corresponding author Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
The present carboxy-appended platinum(ii) complexes exhibit UV-vis and luminescence spectra changes by the protonation/deprotonation trrigered by the addition of acid and base.
DOI： 10.1039/d3dt00956d
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Light-induced excited spin state trapping in iron(iii) complexes Reviewed
Manabu Nakaya, Ryo Ohtani, Leonard F. Lindoy, Shinya Hayami
Inorganic Chemistry Frontiers 8 ( 2 ) 484 - 498 2021
Authorship：Lead author Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
<p>This review discusses the correlation of the local and whole molecular structure of iron(<sc>iii</sc>) complexes with the magnetic properties including the light-induced excited spin-state trapping (LIESST) effect.</p>
DOI： 10.1039/d0qi01188f
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Metal-Dependent DNA Base Pairing of 5-Carboxyuracil with Itself and All Four Canonical Nucleobases Reviewed
Yusuke Takezawa, Akira Suzuki, Manabu Nakaya, Kotaro Nishiyama, Mitsuhiko Shionoya
Journal of the American Chemical Society 142 ( 52 ) 21640 - 21644 2020.12
Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society ({ACS})
DOI： 10.1021/jacs.0c11437
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Guest Modulated Spin States of Metal Complex Assemblies Reviewed
Manabu Nakaya, Ryo Ohtani, Shinya Hayami
European Journal of Inorganic Chemistry 2020 ( 39 ) 3709 - 3719 2020.10
Authorship：Lead author
© 2020 Wiley-VCH GmbH Recently, “host–guest chemistry” aspects of material science have received much attention, particularly in relation to moderating the functions of materials. In particular, magnetic properties involving the “magnetic ordering” and “spin crossover” of host–guest metal complex systems have been actively investigated in terms of their host–guest chemistry. That is, systems in which the magnetic properties are sensitive to perturbation by the uptake of guests (which thus act as chemical stimuli). Such guests (solvents, gases and organic molecules) very often influence the structures of both discrete metallosupramolecular assemblies as well as those of coordination polymers/metal-organic frameworks (CPs/MOFs), providing a means for fine-tuning their magnetic behavior, including the switching of their spin states. In this minireview, we report recent progress in the development and investigation of magnetic materials of both the CP and MOF categories as well as of discrete complexes whose properties are modulated by guests.
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CO2-Induced Spin-State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature Reviewed International journal
Manabu Nakaya, Wataru Kosaka, Hitoshi Miyasaka, Yuki Komatsumaru, Shogo Kawaguchi, Kunihisa Sugimoto, Yingjie Zhang, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami
Angewandte Chemie - International Edition 59 ( 26 ) 10658 - 10655 2020.03
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim CO2-responsive spin-state conversion between high-spin (HS) and low-spin (LS) states at room temperature was achieved in a monomeric cobalt(II) complex. A neutral cobalt(II) complex, [CoII(COO-terpy)2]⋅4 H2O (1⋅4 H2O), stably formed cavities generated via π–π stacking motifs and hydrogen bond networks, resulting in the accommodation of four water molecules. Crystalline 1⋅4 H2O transformed to solvent-free 1 without loss of porosity by heating to 420 K. Compound 1 exhibited a selective CO2 adsorption via a gate-open type of the structural modification. Furthermore, the HS/LS transition temperature (T1/2) was able to be tuned by the CO2 pressure over a wide temperature range. Unlike 1 exhibits the HS state at 290 K, the CO2-accomodated form 1⊃CO2 (P (Formula presented.) =110 kPa) was stabilized in the LS state at 290 K, probably caused by a chemical pressure effect by CO2 accommodation, which provides reversible spin-state conversion by introducing/evacuating CO2 gas into/from 1.
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Giant anisotropic thermal expansion of copper-cyanido flat layers with flexible copper nodes Reviewed
Yuudai Iwai, Manabu Nakaya, Yuta Tsuji, Benjamin Le Ouay, Masaaki Ohba, Ryo Ohtani
Chemical Communications 60 ( 51 ) 6512 - 6515 2024
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
Distorted honeycomb coordination layers are extremely flexible and exhibit giant anisotropic thermal expansion.
DOI： 10.1039/d4cc01232a
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Janus-Type Mixed-Valent Copper–Cyanido Honeycomb Layers Reviewed
Yuudai Iwai, Yuki Imamura, Manabu Nakaya, Miki Inada, Benjamin Le Ouay, Masaaki Ohba, Ryo Ohtani
Inorganic Chemistry 62 ( 45 ) 18707 - 18713 2023.10
Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)
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Sotaro Kusumoto, Kazumasa Inaba, Harutoshi Suda, Manabu Nakaya, Ryuya Tokunaga, Pierre Thuéry, Rie Haruki, Tomoki Kanazawa, Shunsuke Nozawa, Yang Kim, Shinya Hayami, Yoshihiro Koide
Inorganic Chemistry 62 ( 39 ) 16222 - 16227 2023.09
Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)
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Crystal Design for Tuning the Mechanical Flexibilities of M(salophen) Complexes Reviewed
Yoshihiro Sekine, Sotaro Kusumoto, Akira Sugimoto, Manabu Nakaya, Shinya Hayami
Crystal Growth & Design 23 ( 4 ) 2013 - 2017 2023.02
Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)
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A Ferroelectric Metallomesogen Exhibiting Field-Induced Slow Magnetic Relaxation Reviewed
Ryohei Akiyoshi, Hikaru Zenno, Yoshihiro Sekine, Manabu Nakaya, Motoko Akita, Daisuke Kosumi, Leonard F. Lindoy, Shinya Hayami
Chemistry - A European Journal 28 ( 5 ) 2022.01
Publishing type：Research paper (scientific journal)
Magnetoelectric (ME) materials exhibiting coupled electric and magnetic properties are of significant interest because of their potential use in memory storage devices, new sensors, or low-consumption devices. Herein, we report a new category of ME material that shows liquid crystal (LC), ferroelectric (FE), and field-induced single molecule magnet (SMM) behaviors. Co(II) complex incorporating alkyl chains of type [Co(3C16-bzimpy)2](BF4)2 (1; 3C16-bzimpy=2,2’-(4-hexadecyloxy-2,6-diyl)bis(1-hexadecyl-1H-benzo[d]imidazole)) displayed a chiral smectic C mesophase in the temperature range 321 K–458 K, in which distinct FE behavior was observed, with a remnant polarization (88.3 nC cm−2). Complex 1 also exhibited field-induced slow magnetic relaxation behavior that reflects the large magnetic anisotropy of the Co(II) center. Furthermore, the dielectric property of 1 was able to be tuned by an external magnetic field occurring from both spin-lattice coupling and molecular orientational variation. Clearly, this multifunctional compound, combining LC, FE, and SMM properties, represents an entry to the development of a range of next-generation ME materials.
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Modulation of the elasticity of single crystal, 1-D metal dimethylglyoximato complexes via solid solution effect Reviewed
Akira Sugimoto, Sotaro Kusumoto, Manabu Nakaya, Yoshihiro Sekine, Leonard F. Lindoy, Shinya Hayami
CrystEngComm 24 ( 26 ) 4656 - 4660 2022
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry ({RSC})
The fabrication of single crystal material with a desired degree of flexibility is a challenging topic in material science and crystal engineering. In this communication, we demonstrate the modulation of elasticity via a solid solution effect occurring in single crystals of one-dimensional, heterometal chain complexes.
DOI： 10.1039/D2CE00402J
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Multi-faceted elastic flexibility of 1-naphthyl and 9-anthryl 2,2′:6′,2′′-terpyridine crystals Reviewed
Sotaro Kusumoto, Karin Oishi, Manabu Nakaya, Ryo Suzuki, Masaru Tachibana, Yang Kim, Yoshihiro Koide, Shinya Hayami
CrystEngComm 24 ( 47 ) 8303 - 8308 2022
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
We report two organic crystals of 2,2′:6′,2′′-terpyridine derivatives each substituted with luminescent naphthyl and anthryl moieties, displaying multi-faceted flexible bending with elasticity in response to mechanical stress.
DOI： 10.1039/d2ce01167k
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Zero area thermal expansion of honeycomb layers via double distortion relaxation in (PPh4)[Cu2(CN)3] Reviewed
Yuudai Iwai, Manabu Nakaya, Hiroyoshi Ohtsu, Benjamin Le Ouay, Ryo Ohtani, Masaaki Ohba
CrystEngComm 24 ( 33 ) 5880 - 5884 2022
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
The zero area TE of cyanide-bridged honeycomb layers occurs by complementary structural changes in the cation and anion counterparts.
DOI： 10.1039/d2ce00878e
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Magnetism in a helicate complexes arising with the tetradentate ligand Reviewed
Hitomi Ohmagari, Manabu Nakaya, Kaisei Tanaka, Hikaru Zenno, Ryohei Akiyoshi, Yoshihiro Sekine, Yingjie Zhang, Kil Sik Min, Miki Hasegawa, Leonard F. Lindoy, Shinya Hayami
Dalton Transactions 50 ( 2 ) 494 - 498 2021
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
<p>The synthesis of [M(dimphen)(NCS)2] (MII = Fe (<bold>1</bold>), Co (<bold>2</bold>), Mn (<bold>3</bold>)) and [Fe(dimphen)(NCSe)2] (<bold>4</bold>), where dimphen = [1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane], are reported. <bold>1</bold> shows ferromagnetic interaction, and <bold>2</bold> displays single-molecular magnet behaviour.</p>
DOI： 10.1039/d0dt03990j
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Yuta Shudo, Md. Saidul Islam, Hikaru Zenno, Masahiro Fukuda, Manabu Nakaya, Nurun Nahar Rabin, Yoshihiro Sekine, Leonard F. Lindoy, Shinya Hayami
Physical Chemistry Chemical Physics 23 ( 42 ) 24233 - 24238 2021
Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)
The tunable ferromagnetic transition behaviors of Ni(OH)2 sheets layered between rGO/GO sheets have been demonstrated.
DOI： 10.1039/d1cp03387e
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Manabu Nakaya, Ryo Ohtani, Jong Won Shin, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami
Dalton Transactions 47 ( 39 ) 13809 - 13814 2018.08
Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)
© 2018 The Royal Society of Chemistry. The cobalt(ii) complex incorporating π-conjugated substituent, [Co(Naph-C2-terpy)2](BF4)2 (1; Naph-C2-terpy = 4′-(2-naphthoxy(ethoxy))-2,2′:6′,2′′-terpyridine), exhibits an abrupt spin transition (ST) behavior (cooperative factor C = 0.91) while its solvated product, 1·2MeOH, shows gradual spin crossover (SCO) behavior (C = 0.49). Single crystal X-ray structural analyses demonstrated that the octahedral coordination core [CoN6] in 1 shows larger distortion in both high-spin and low-spin states than solvated 1·2MeOH or another two derivatives, [Co(R-terpy)2](BF4)2 (R = 2-naphthyl (2), 9-anthracenyl (3)). The respective distortion parameters (Σ) are compared with those for previously reported SCO cobalt(ii) compounds. The highly-distorted [CoN6] core in 1 (Σ = 126 in the HS state and 101.6 in the LS state) was stabilized by strong intermolecular interactions and observed an abrupt ST behaviour.
DOI： 10.1039/C8DT02367K
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Post-synthetic modification of a dinuclear spin crossover iron(III) complex Reviewed
Yuki Komatsumaru, Manabu Nakaya, Fumiya Kobayashi, Ryo Ohtani, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami
Zeitschrift für anorganische und allgemeine Chemie 2018.08
Language：English Publishing type：Research paper (scientific journal) Publisher：Wiley-VCH
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Post-synthetic Modification of a Dinuclear Spin Crossover Iron(III) Complex Reviewed
Yuki Komatsumaru, Manabu Nakaya, Fumiya Kobayashi, Ryo Ohtani, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami
Zeitschrift fur Anorganische und Allgemeine Chemie 644 ( 14 ) 729 - 734 2018.08
Language：English Publishing type：Research paper (scientific journal)
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The dinuclear iron(III) complex [Fe(salten)2(bipytz)](BPh4)2·EtOH (1) was synthesized and its post-synthesis modification yielded [Fe(salten)2(bipydz)](BPh4)2·EtOH (2). The crystal structures and magnetic behaviors of 1 and 2 were investigated by variable temperature XRD, magnetic susceptibility, and Mössbauer spectra measurements, with each of these dinuclear iron(III) complexes exhibiting gradual spin crossover behavior.
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Intermolecular Interaction Tuning of Spin-Crossover Iron(III) Complexes with Aromatic Counteranions Reviewed
Asami Tsukiashi, Manabu Nakaya, Fumiya Kobayashi, Ryo Ohtani, Masaaki Nakamura, Jack M. Harrowfield, Yang Kim, Shinya Hayami
Inorganic Chemistry 57 ( 5 ) 2834 - 2842 2018.02
Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society
© 2018 American Chemical Society. Iron(III) spin-crossover (SCO) complexes [Fe(qsal)2]BS·MeOH·H2O (1), [Fe(qsal)2](NS)·MeOH (2), [Fe(qnal)2](NS) (3), and [Fe(qnal)2]PS·MeOH·CH2Cl2 (4) (Hqsal, N-(8-quinolinyl)salicylaldimine; Hqnal, N-(8-quinolinyl)-2-hydroxy-1-naphthaldimine; BS, benzenesulfonate; NS, 1-naphthalenesulfonate; PS, 1-pyrenesulfonate) have been synthesized and characterized by X-ray structure determinations and temperature-dependent magnetic susceptibility measurements. The aromatic counteranions BS, NS, and PS can be used for the tuning of intermolecular coupling through a variety of weak interactions. All of the complexes show temperature-dependent SCO behavior. but the light-induced excited spin-state trapping (LIESST) effect was observed only for 1, 3, and 4 when the samples were illuminated (λ 808 nm) for 1 h at 5 K. In particular, 59% of the LS form of 1 was converted to the metastable HS state by illumination, equal to the highest degree of conversion yet known for LIESST in [Fe(qsal)2]+ derivatives. The lack of a LIESST effect for 2 may be due to the relatively limited degree of interaction between the cations and anions in the lattice, reflected in a much longer minimum Fe···Fe separation in this complex in comparison to the others.