Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
Shinji Kanegawa Last modified date:2020.05.29

Assistant Professor / Department of Fundamental Organic Chemistry / Institute for Materials Chemistry and Engineering


Papers
1. Junqiu Li, Shuqi Wu, Shengqun Su, Shinji Kanegawa, Osamu Sato, Manipulating Slow Magnetic Relaxation by Light in a Charge Transfer {Fe2Co} Complex, Chemistry - A European Journal, 10.1002/chem.202000154, 26, 15, 3259-3263, 2020.03, Some cyanide-bridged complexes are known for exhibiting slow magnetic relaxation behavior in a light-induced metastable state. Herein, an unexpected reverse effect is observed for the first time in the S= (Formula presented.) {FeII LS-CoIII LS-FeIII LS} (HS=high spin, LS=low spin) ground state of a novel V-shaped trinuclear cyanide-bridged {Fe2Co} complex. In this complex, light-switchable iron-cobalt charge transfer with repeatable off/on switching of slow magnetic relaxation is discovered upon alternating laser irradiation at 785 and 560 nm. An important characteristic of the present compound is that the S= (Formula presented.) ground state exhibits slow magnetic relaxation before irradiation, whereas this is accelerated after irradiation. This is different from the typical behavior, where the light-induced metastable state exhibits slow magnetic relaxation..
2. Wei Huang, Shuqi Wu, Xiangwei Gu, Yao Li, Atsushi Okazawa, Norimichi Kojima, Shinya Hayami, Michael L. Baker, Peter Bencok, Mariko Noguchi, Yuji Miyazaki, Motohiro Nakano, Takumi Nakanishi, Shinji Kanegawa, Yuji Inagaki, Tatsuya Kawae, Gui Lin Zhuang, Yoshihito Shiota, Kazunari Yoshizawa, Dayu Wu, Osamu Sato, Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex, Nature communications, 10.1038/s41467-019-13279-y, 10, 1, 2019.12, The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex..
3. Narita, Masahiro; Teraoka, Takaaki; Murafuji, Toshihiro; Shiota, Yoshihito; Yoshizawa, Kazunari; Mori, Shigeki; Uno, Hidemitsu; Kanegawa, Shinji; Sato, Osamu; Goto, Kenta; Tani, Fumito, An Azulene-Based Chiral Helicene and Its Air-Stable Cation Radical, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 10.1246/bcsj.20190219, 92, 11, 1867-1873, 2019.11.
4. Takahiro Inatomi, Yukino Fukahori, Yuji Yamada, Ryuta Ishikawa, Shinji Kanegawa, Yuji Koga, Kouki Matsubara, Ni(i)-Ni(iii) cycle in Buchwald-Hartwig amination of aryl bromide mediated by NHC-ligated Ni(i) complexes, Catalysis Science and Technology, 10.1039/c8cy02427h, 9, 8, 1784-1793, 2019.01, Intermediate amide complexes of NHC-ligated monovalent nickel in Buchwald-Hartwig amination of aryl halides were isolated and structurally characterized. The amide complexes reacted with aryl bromide to form a cross-coupling product. Lowerature observation of the oxidative addition product of the Ni(i) amide complex with aryl bromide indicated the presence of a Ni(iii) intermediate. The results showed that a well-defined mononuclear NHC-Ni(i) complex can act as a key intermediate in homogeneous catalysis..
5. Kouki Matsubara, Yukino Fukahori, Takahiro Inatomi, Saeko Tazaki, Yuji Yamada, Yuji Koga, Shinji Kanegawa, Toshikazu Nakamura, Monomeric three-coordinate N-heterocyclic carbene nickel(I) complexes
Synthesis, structures, and catalytic applications in cross-coupling reactions, Organometallics, 10.1021/acs.organomet.6b00419, 35, 19, 3281-3287, 2016.10, A series of three-coordinate monovalent nickel halide complexes bearing N-heterocyclic carbene (NHC) ligands, i.e., NiCl(IPr)(L) [L = pyridine, P(OPh)3, bis(diphenylphosphino)butane (dppb), IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], NiX(IMes)(PPh3) (X = Cl and Br, IMes = 1,3-bis(mesityl)imidazol-2-ylidene), were prepared. The complexes were identified using NMR spectroscopy, superconducting quantum interference device (SQUID), and X-ray crystallography. Additionally, ESR spectra of NiCl(IPr)(pyridine) were taken in toluene. These complexes had three-coordinate Y-shaped geometries in both the solid and solution states. The compounds containing IPr showed equilibrium between the monomeric and dimeric forms, with liberation of ligands. Addition of 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane to the dinickel(I) IPr complex instead of dppb resulted in heterolytic cleavage to nickel(0) and nickel(II) species. Catalysis of Suzuki cross-coupling and Buchwald-Hartwig amination of aryl bromide using the complexes was investigated. The efficiencies in the amination of aryl bromide depended strongly on the additional donor ligands..
6. Soonchul Kang, Yoshihito Shiota, Akira Kariyazaki, Shinji Kanegawa, Kazunari Yoshizawa, Osamu Sato, Frontispiece
Heterometallic FeIII/K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature, Chemistry - A European Journal, 10.1002/chem.201680262, 22, 2, 2016.01, The FeIII anionic complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2] (5-Brthsa-H2=5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis shows the coexistence of hydrogen bond and cation-π interactions, along with metal coordination bonds, to give 2D coordination polymer structure..
7. KANG SOONCHUL, 金川 慎治, 塩田 淑仁, 吉澤 一成, 佐藤 治, A ferromagnetically coupled Fe-42 cyanide-bridged nanocage, Nature Communications, 10.1038/ncomms6955, 6, 2015.01.
8. Zi Shuo Yao, Masaki Mito, Takashi Kamachi, Yoshihito Shiota, Kazunari Yoshizawa, Nobuaki Azuma, Yuji Miyazaki, Kazuyuki Takahashi, Kuirun Zhang, Takumi Nakanishi, Soonchul Kang, Shinji Kanegawa, Osamu Sato, Molecular motor-driven abrupt anisotropic shape change in a single crystal of a Ni complex, Nature Chemistry, 10.1038/nchem.2092, 6, 12, 1079-1083, 2014.01, Many molecular machines with controllable molecular-scale motors have been developed. However, transmitting molecular movement to the macroscopic scale remains a formidable challenge. Here we report a single crystal of a Ni complex whose shape changes abruptly and reversibly in response to thermal changes at around room temperature. Variableerature single-crystal X-ray diffraction studies show that the crystalline shape change is induced by an unusual 90° rotation of uniaxially aligned oxalate molecules. The oxalate dianions behave as molecular-scale rotors, with their movement propagated through the entire crystalline material via intermolecular hydrogen bonding. Consequently, the subnanometre-scale changes in the oxalate molecules are instantly amplified to a micrometre-scale contraction or expansion of the crystal, accompanied by a thermal hysteresis loop. The shape change in the crystal was clearly detected under an optical microscope. The large directional deformation and prompt response suggest a role for this material in microscale or nanoscale thermal actuators..
9. Tao Liu, Hui Zheng, KANG SOONCHUL, Yoshihito Shiota, Shinya Hayami, Masaki Mito, Osamu Sato, Kazunari Yoshizawa, Shinji Kanegawa, Chunying Duan, A light-induced spin crossover actuated single-chain magnet, NATURE COMMUNICATIONS, 10.1038/ncomms3826, 4, 2013.11, Both spin-crossover complexes and molecular nanomagnets display bistable magnetic states, potentially behaving as elementary binary units for information storage. It is a challenge to introduce spin-crossover units into molecular nanomagnets to switch the bistable state of the nanomagnets through external stimuli-tuned spin crossover. Here we report an iron(II) spin-crossover unit and paramagnetic iron(III) ions that are incorporated into a well-isolated double-zigzag chain. The chain exhibits thermally induced reversible spin-crossover and light-induced excited spin-state trapping at the iron(II) sites. Single-chain magnet behaviour is actuated accompanying the synergy between light-induced excited spin-state trapping at the iron(II) sites and ferromagnetic interactions between the photoinduced high-spin iron(II) and low-spin iron(III) ions in the chain. The result provides a strategy to switch the bistable state of molecular nanomagnets using external stimuli such as light and heat, with the potential to erase and write information at a molecular level..
10. Zhao Yang Li, Jing Wei Dai, Kevin J. Gagnon, Hong Ling Cai, Takashi Yamamoto, Yasuaki Einaga, Han Hua Zhao, Shinji Kanegawa, Osamu Sato, Kim R. Dunbar, Ren Gen Xiong, A neutral Fe(iii) compound exhibiting a two-step spin transition and dielectric anomalies, Dalton Transactions, 10.1039/c3dt51554k, 42, 41, 14685-14688, 2013.11, The mononuclear ferric compound Fe(H-5-Cl-thsa-Me)(5-Cl-thsa-Me) ·H2O (1) was synthesized and characterized using powder/single-crystal X-ray diffraction, Mössbauer spectroscopy, differential scanning calorimetry (DSC), and magnetic susceptibility measurements. This photo-responsive compound shows reversible, two-step spin-crossover behaviour. Moreover, dielectric anomalies were observed during the spin transitions, demonstrating the multifunctional properties of compound 1..
11. Zhao-Yang Li, Jing-Wei Dai, Yoshihito Shiota, Kazunari Yoshizawa, Shinji Kanegawa, Osamu Sato, Multi-Step Spin Crossover Accompanied by Symmetry Breaking in an Fe-III Complex: Crystallographic Evidence and DFT Studies, CHEMISTRY-A EUROPEAN JOURNAL, 10.1002/chem.201302272, 19, 39, 12948-12952, 2013.09.
12. Dai Jingwei, Shinji Kanegawa, Li Zhaoyang, KANG SOONCHUL, Osamu Sato, A Switchable Complex Ligand Exhibiting Photoinduced Valence Tautomerism, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 10.1002/ejic.201300531, 2013, 24, 4150-4153, 2013.08.
13. Shinji Kanegawa, KANG SOONCHUL, Osamu Sato, Preparation and Valence Tautomeric Behavior of a Cobalt-Dioxolene Complex with a New TTF-functionalized Phenanthroline Ligand, CHEMISTRY LETTERS, 10.1246/cl.130118, 42, 7, 700-702, 2013.07.
14. Atsushi Tashiro, Shinji Kanegawa, Osamu Sato, Yoshio Teki, ESR study of light-induced valence tautomerism of a Co mononuclear complex
[Co(phen)(3,5-DTBSQ)(3,5-DTBCat)], Polyhedron, 10.1016/j.poly.2013.03.039, 66, 167-170, 2013.04, Light-induced valence tautomerism (LIVT) and the relaxation process of a mononuclear complex, [Co(phen)(3,5-DTBSQ)(3,5-DTBCat)] (1) (phen = 1,10-phenanthroline, 3,5-DTBSQ = 3,5-di-tert-butyl-semiquinone, 3,5-DTBCat = 3,5-di-tert-butyl-catechol) were investigated by monitoring the ESR signal of the semiquinonate radical both in powder sample and in the sample diluted in butyronitrile or benzene glass matrix. LIVT phenomena were observed in all samples. The ESR signal decay and the relaxation in the glass matrixes were well analyzed by double exponential fitting, indicating the possibility of two-step mechanism in the LIVT process..
15. Shinji Kanegawa, KANG SOONCHUL, Osamu Sato, Spin Crossover Behavior of Dinuclear Fe-II Complexes with Bis-Tetradentate Bridging-Type Ligands, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 10.1002/ejic.201201069, 5-6, 725-729, 2013.02.
16. Zhao Yang Li, Osamu Sato, Zi Shuo Yao, Soonchul Kang, Shinji Kanegawa, Multifunctional Materials Combining Spin-Crossover with Conductivity and Magnetic Ordering, Spin-Crossover Materials: Properties and Applications, 10.1002/9781118519301.ch11, 303-319, 2013.01, This chapter introduces compounds synthesized to develop new spin-crossover conductors, in which spin-crossover phenomena and conductivity coexist or interact. It also introduces spin-crossover magnets, in which spin-crossover phenomena and magnetic interaction coexist or interact. A possible route for the synthesis of multifunctional materials exhibiting spin-crossover and conductivity is the preparation of double salts, by combining spin-crossover cations/anions and conducting molecular anions/cations through electrostatic interactions. Another route is the preparation of a spin-crossover complex with a potentially conducting ligand. The preparation of spin-crossover conductors in which conductivity and light-induced excited spin state trapping (LIESST) exhibit synergistic effects is desired. Multifunctional materials exhibiting both spin-crossover and magnetic interaction are achieved by combining a spin-crossover cation/anion with an anionic/cationic magnetic framework. Another route is the incorporation of spin-crossover sites into magnetic frameworks. This edition first published 2013.
17. KANG SOONCHUL, Shinji Kanegawa, Osamu Sato, Slow magnetic relaxation in a 4,2-ribbon like Fe-III Co-2(II) heterobimetallic chain, DALTON TRANSACTIONS, 10.1039/c2dt31168b, 41, 44, 13575-13577, 2012.09.
18. Kensuke Murashima, Takeaki Watanabe, Shinji Kanegawa, Daisuke Yoshihara, Yuji Inagaki, Satoru Karasawa, Noboru Koga, Preparations, crystal structures, and magnetic properties of N, N-dipyridylaminoxyl as a new magnetic coupler and its one-dimensional cobalt(II) chains, Inorganic chemistry, 10.1021/ic202397m, 51, 9, 4982-4993, 2012.05, N,N-Dipyridilaminoxyl, NOpy 2, having a stable aminoxyl, was prepared as a new magnetic coupler for heterospin systems. Solutions of NOpy 2 were mixed with those of bis{1,1,1,5,5,5, hexafluoro-4- (phenylimino)-2-pentanonate}cobalt derivatives, Co(hfpip-X) 2, at a 1:1 ratio to afford the polymeric cobalt(II) complexes, [Co(hfpip-X) 2(NOpy 2)] n; X = H (1), F (2), F 3 (3), F 5 (4), Cl (5), Cl 3 (6), Br (7), and I (8) as single crystals. In all complexes, the local structures of the cobalt-complex units were compressed octahedra and the pyridine ligands in NOpy 2 units coordinated to the cobalt ions in trans configuration to form linear chains for 1-4 and in cis configuration to form helical chains for 5-8. In the chains, the aminoxyl in NOpy 2 ferromagnetically interacted with the cobalt ions to produce the ferromagnetic chains with J intra/k B = 9-14 K. In the magnetic susceptibility experiments of aligned sample of 6, the magnetic easy axis was determined to be the a* axis, which was the direction perpendicular to the b axis of the chain axis. The resulting chains, all except 4, interacted antiferromagnetically among each other, and especially in 1, 5, 7, and 8, the magnetic behaviors characteristic to canted two-dimensional (2D) antiferromagnets with T c = 5.6, 4.0, 4.0, and 6.2 K, respectively, were observed. All complexes showed slow magnetic relaxations affected by the interchain antiferromagnetic interaction. The effective activation barriers, Δ eff/k B, for the reorientation of the magnetism for all complexes except 4 were estimated to be 25-39 K in the presence of a direct current (dc) field..
19. Dong, DP; Liu, T; Kanegawa, S; Kang, S; Sato, O; He, C ; Duan, CY, Photoswitchable Dynamic Magnetic Relaxation in a Well-Isolated {Fe2Co} Double-Zigzag Chain, Angewandte Chemie International Edition, 10.1002/anie.201105987, 52, 21, 5119, 2012.04, Charge-transfer-induced spin transition occurs cooperatively and reversibly in the isolated FeIII2CoII chains of {[Fe(pzTp)(CN)3]2Co(4-styrylpyridine)2}⋅2 H2O ⋅2 CH3OH (1). When 1 is irradiated with 532 nm light, it shows single-chain magnetic behavior with no antiferromagnetic ordering after irradiation (see picture; C gray, N blue, B yellow; LS=low spin, HS=high spin)..
20. Liu, T; Dong, DP; Kanegawa, S; Kang, S; Sato, O; Shiota, Y; Yoshizawa, K; Hayami, S; Wu, S; He, C; Duan, CY , Reversible Electron Transfer in a Linear {Fe2Co} Trinuclear Complex Induced by Thermal Treatment and Photoirraditaion, Angewandte Chemie International Edition, 10.1002/anie.201201305, 51, 18, 4367, 2012.03, A linear cyanido-bridged Fe2Co compound (see picture) exhibits a reversible, thermally induced cooperative charge transfer transition accompanying spin transition and polar–nonpolar transformation in the trinuclear cluster. The change in magnetic properties and polarity could also be induced by irradiation with light..
21. Yoshio Teki, Mugen Shirokoshi, Shinji Kanegawa, Osamu Sato, ESR study of light-induced valence tautomerism of a dinuclear Co complex, European Journal of Inorganic Chemistry, 10.1002/ejic.201100467, 25, 3761-3767, 2011.09, Light-induced valence tautomerism (LIVT) of a dinuclear complex, [{Co(dpqa)}2(dhbq)](PF6)3 (1), was investigated by ESR analysis of dhbq3-. LIVT phenomena were observed in the sample diluted in the glass matrix as well as that in powder form. The signal decay and the relaxation were analyzed by double exponential fitting; the results suggest a two-step mechanism. Quantum mechanical tunneling was clearly observed in the glass matrix. Light-induced valence tautomerism (LIVT) of a dinuclear complex, [{Co(dpqa)}2(dhbq)](PF6)3 (1), was investigated by ESR analysis of dhbq3-. LIVT phenomena were observed in the glass matrix as well as in the powder sample. The signal decay and the relaxation, analyzed by double exponential fitting, suggest a two-step mechanism. Quantum tunneling phenomena were clearly observed in the glass matrix..
22. H. Xu, G. Juhász, K. Yoshizawa, M. Takahashi, S. Kanegawa, *O. Sato,, “Mixed-metal complex [Fe(bipe)(Au(CN)2)2MeOH] with gold clusters: a novel two-dimensional polyrotaxane net clipped by aurophilic interaction”, CrystEngComm, 12, 4045-4047, 2011.06.
23. Haitao Xu, Gergely Juhász, Kazunari Yoshizawa, Masashi Takahashi, Shinji Kanegawa, Osamu Sato, Mixed-metal complex [Fe(bipe)(Au(CN)2)2·MeOH] with gold clusters
A novel two-dimensional polyrotaxane net clipped by aurophilic interaction, CrystEngComm, 10.1039/c0ce00376j, 12, 12, 4031-4034, 2010.12, A novel two-dimensional mixed-metal coordination polymer, [Fe(bipe)(Au(CN)2)2·MeOH], composed of polyrotaxane with Fe2(bipe)2 loops and rigid [Au(CN)2] - rods, forms a 2D → 2D parallel interpenetrating structure. The two networks are clipped by gold clusters via aurophilic interaction..
24. T. Liu, Y.-J. Zhang, S. Kanegawa, *O. Sato, Water-Switching of Spin Transitions Induced by Metal-to-Metal Charge Transfer in a Microporous Framework, Angew. Chem. Int. Ed., 10.1002/anie.201002881, 49, 46, 8645-8648, 2010.11.
25. Liu, T; Zhang, YJ; Kanegawa, S; Sato, O, Photoinduced Metal-to-Metal Charge Transfer toward Single-Chain Magnet, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/ja1027953, 132, 24, 8250, 2010.06.
26. Zhang Yan-Juan, Liu Tao, Kanegawa Shinji, Sato Osamu, Interconversion between a Nonporous Nanocluster and a Microporous Coordination Polymer Showing Selective Gas Adsorption, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/ja908670u, 132, 3, 912, 2010.01.
27. Zhang, Yan-Juan, Liu, Tao, Kanegawa, Shinji, Sato, Osamu, Reversible Single-Crystal-to-Single-Crystal Transformation from Achiral Antiferromagnetic Hexanuclears to a Chiral Ferrimagnetic Double Zigzag Chain , Journal of the American Chemical Society, 10.1021/ja901539y, 131, 23, 7942, 2009.06.
28. Gergely Juhsz, Ryotaro Matsuda, Shinji Kanegawa, Kaori Inoue, Osamu Sato* and Kazunari Yoshizawa, Bistability of Magnetization without Spin-Transition in a High-Spin Cobalt(II) Complex due to Angular Momentum Quenching , Journal of the American Chemical Society, 10.1021/ja808448j, 131, 13, 4560, 2009.04.
29. Shinji Kanegawa, Satoru Karasawa, Masataka Maeyama, Motohiro Nakano, and Noboru Koga, Crystal Design of Monometallic Single-Molecule Magnets Consisting of Cobalt-Aminoxyl Heterospins, Journal of the American Chemical Society, 10.1021/ja0767579, 130, 10, 3079-3094, 2008.03.
30. Shinji Kanegawa, Satoru Karasawa, Motohiro Nakano, Noboru Koga, Magnetic properties of 1:4 complexes of CoIIX2(X = NCO -, NCS -, and Br -) with 4-(N-tert- butylaminoxyl)pyridine. Antiferromagnets in crystalline states and single-molecule magnets in frozen solutions, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.79.1372, 79, 9, 1372-1382, 2006.09, Three cobalt(II) complexes, [Co(X) 2(4NOpy) 4] (X = NCO -, NCS -, and Br -; 4NOpy = 4-(N-tert-butylaminoxyl)-pyridine) were prepared, and their molecular structures were characterized by X-ray structure analysis. The molecular geometry of [Co(X) 2(4NOpy) 4] (X = NCO - and NCS -) is a compressed octahedron, in which the counter ions occupy the apical positions with short bond distances of 2.064-2.098 Å. In the crystalline state, from plots of χ mol vs T and χ′ mol vs T, [Co(NCO) 2(4NOpy) 4] and [Co(NCS) 2(4NOpy) 4] are antiferromagnets with T N = 4.5 and 15 K, respectively. In frozen solution, on the other hand, both complexes and [Co(Br) 2(4NOpy) 4] functioned as single-molecule magnets. The χ″ mol vs T plot for [Co(Br) 2(4NOpy) 4] gave a effective activation barrier (U eff) of 20 K for the reorientation of the spin. From the field dependence of magnetization at various temperatures below 5 K for [Co(X) 2(4NOpy) 4] (X = NCO -, NCS -, and Br -) the values of the zero-field splitting parameters, D/k B, were estimated to be -14, -9.7, and -4.5 K with S = 5/2, respectively. Theoretical studies based on the ligand-field theory model for [Co(NCO) 2(4NOpy) 4] gave an exchange coupling parameter, J/k B, of 29 K and a thermodynamic activation barrier, U, of 60 K..