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堀井　洋司Horii Yojiホリイ　ヨウジ

■所属部署名研究院自然科学系化学領域
■職名助教
Last Updated :2023/08/02

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プロフィール情報

  • 姓

    堀井, ホリイ

  • 名

    洋司, ヨウジ

学位

  • 博士（理学）, 東北大学

研究分野

  • 自然科学一般, 生物物理、化学物理、ソフトマターの物理

Ⅱ．研究活動実績

論文

  • 査読あり, その他, European Journal of Inorganic Chemistry, Slow Magnetic Relaxations of Ni(III) Complexes Toward Molecular Spin Qubits, Keiga Toshima; Tetsu Sato; Yoji Horii; Kazunobu Sato; Kenji Sugisaki; Brian Breedlove; Shinya Takaishi; Zhao-Yang Li; Masahiro Yamashita, 2023年03月30日, 研究論文（学術雑誌）, 10.1002/ejic.202300125
  • 査読あり, その他, The Journal of Physical Chemistry C, Slow Magnetic Relaxation of Linear Trinuclear M(II)–Gd(III)–M(II) Complexes with D3 Point Group Symmetry (M(II) = Zn(II) and Mg(II)), Yuka Masuda; Shiomi Sakata; Saori Kayahara; Natsumi Irie; Maiko Kofu; Yohei Kono; Toshiro Sakakibara; Yoji Horii; Takashi Kajiwara, 2023年02月06日, 研究論文（学術雑誌）, 10.1021/acs.jpcc.2c08323
  • 査読あり, その他, Journal of Materials Chemistry C, Construction of a two-dimensional metal-organic framework with a perpendicular magnetic anisotropy composed of single-molecule magnets, Ikumi Aratani; Yoji Horii; Daisuke Takajo; Yoshinori Kotani; Hitoshi Osawa; Takashi Kajiwara, The use of single-molecule magnets (SMMs) as memory devices can dramatically increase information storage capacity. However, a regular array of SMMs needs to be constructed on a substrate to access..., 2023年, 研究論文（学術雑誌）, 10.1039/d2tc04963e
  • 査読あり, その他, ACS Applied Polymer Materials, Defect-Assisted High Anion Conductivity in Diethyldimethylammonium d-Camphorsulfonate Plastic Crystal: A Size Effect of Target Ions, Xue Lan; Wenjing Sun; Xin Wang; Wei Xu; Yoji Horii; Jiandang Liu; Hongjun Zhang; Bangjiao Ye; Tiancheng Mu; Xiaozheng Lan, 2022年11月07日, 研究論文（学術雑誌）, 10.1021/acsapm.2c01616
  • 査読あり, その他, Chemical Society Reviews, Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications, Alexander G. Martynov; Yoji Horii; Keiichi Katoh; Yongzhong Bian; Jianzhuang Jiang; Masahiro Yamashita; Yulia G. Gorbunova, This review summarises advances in chemistry of tetrapyrrole sandwiches with rare earth elements and highlights the current state of their use in single-molecule magnetism, organic field-effect transistors, conducting materials and nonlinear optics., 2022年10月31日, 研究論文（学術雑誌）, 10.1039/d2cs00559j
  • 査読あり, その他, ChemPhysChem, Porous Mn2+ Magnet with a Pt–Cl Framework: Correlation between Water Vapor Adsorption/Desorption and Slow Magnetic Relaxation, Hirotaka Nakajima; Kaiji Uchida; Takefumi Yoshida; Yoji Horii; Tetsu Sato; Zhang Luming; Satoshi Yamashita; Yasuhiro Nakazawa; Verdad C. Agulto; Makoto Nakajima; Brian K. Breedlove; Masahiro Yamashita; Hiroaki Iguchi; Shinya Takaishi, 2022年10月26日, 研究論文（学術雑誌）, 10.1002/cphc.202200618
  • 査読あり, その他, ChemPhysChem, Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array, Shohei Koyama; Yoji Horii; Tetsu Sato; Shinya Takaishi; Norihisa Hoshino; Tomoyuki Akutagawa; Hiroaki Iguchi, 2022年10月06日, 23, 19, 研究論文（学術雑誌）, 10.1002/cphc.202200322
  • 査読あり, 英語, Inorganic Chemistry Frontiers, Solid polymorphism and dynamic magnetic properties of dodecylated vanadyl-porphyrinato complex: Spin-lattice relaxations modulated by phase stabilisation, Yoji Horii; Momo Makino; Taro Yamamoto; Shoichi Tatsumi; Hal Suzuki; Mariko Noguchi; Takefumi Yoshida; Takashi Kajiwara; Zhaoyang Li; Masahiro Yamashita, The dynamical magnetic behavior of metal complexes correlates with their phonon modes, which depend on solid polymorphs. However, no systematic study has revealed the correlation between solid phases and spin-lattice..., 2022年10月, 研究論文（学術雑誌）, 10.1039/d2qi01607a
  • 査読あり, 英語, Dalton transactions, Structural, magnetic and theoretical analyses of anionic and cationic phthalocyaninato-terbium(III) double-decker complexes: magnetic relaxation via higher ligand-field sublevels enhanced by oxidation., Yoji Horii; Marko Damjanović; Keiichi Katoh; Masahiro Yamashita, Crystal structural and magnetic analyses were performed for the anionic (1-) and cationic (1+) forms of phthalocyaninato-Tb3+ double-decker single-molecule magnets (SMMs). Both charged species showed slow magnetic relaxations and magnetic hysteresis characteristics for SMMs. 1+ showed longer magnetic relaxation times (τ) and higher activation energy for spin reversal (ΔE) than 1- did. Ligand field (LF) splitting calculated using ab initio methods revealed that the experimental ΔE values in 1- and 1+ were considerably larger than the first excited LF levels but rather close to the higher excited ones, indicating the magnetic relaxation via higher excited states., 2021年07月21日, 50, 28, 9719, 9724, 研究論文（学術雑誌）, 国際誌, 10.1039/d1dt00775k
  • 査読あり, 英語, Physical chemistry chemical physics : PCCP, Dynamics and magnetic properties of NO molecules encapsulated in open-cage fullerene derivatives evidenced by low temperature heat capacity., Yoji Horii; Hal Suzuki; Yuji Miyazaki; Motohiro Nakano; Shota Hasegawa; Yoshifumi Hashikawa; Yasujiro Murata, Low-temperature heat capacity analyses for an NO-encapsulated fullerene derivative revealed (i) low-energy motion and (ii) strong magnetic anisotropy of the NO molecule due to its orbital angular momentum. The low-energy motion was attributed to reorientational motions of the NO molecules, in which only a small number (n ∼ 0.04) of NO molecules were found to participate. The NO molecules were confirmed to be paramagnetic even at 1 K. Ab-initio calculation indicated that the magnetic properties of the NO unit strongly depended on its surroundings, allowing the conformation of the fullerene cage to be estimated., 2021年04月26日, 研究論文（学術雑誌）, 国際誌, 10.1039/d1cp00482d
  • 査読あり, 英語, Bulletin of the Chemical Society of Japan, Insight into the Gd–Pt Bond: Slow Magnetic Relaxation of a Heterometallic Gd–Pt Complex, Takefumi Yoshida; Ahmed Shabana; Haitao Zhang; David Chukwuma Izuogu; Tetsu Sato; Kentaro Fuku; Hitoshi Abe; Yoji Horii; Goulven Cosquer; Norihisa Hoshino; Tomoyuki Akutagawa; Alex J. W. Thom; Shinya Takaishi; Masahiro Yamashita, 2022年02月10日, 95, 3, 513, 521, 研究論文（学術雑誌）, 10.1246/bcsj.20210429
  • 査読あり, 英語, Dalton Transactions, Comparison between DySc2N@C80 and Dy2ScN@C80 single-molecule magnetic metallofullerenes encapsulated in single-wall carbon nanotubes, Satoshi Ito; Ryo Nakanishi; Keiichi Katoh; Brian K. Breedlove; Tetsu Sato; Zhao-Yang Li; Yoji Horii; Masanori Wakizaka; Masahiro Yamashita, The quantum tunneling mechanism of DySc2N@C80 and Dy2ScN@C80 in single-walled carbon nanotubes was revealed to be tuned in opposite ways., 2022年03月25日, 51, 16, 6339, 6344, 研究論文（学術雑誌）, 国際誌, 10.1039/d2dt00524g
  • 査読あり, 英語, Inorganic chemistry, Solid-State Spin Equilibrium of Ni(cyclam)2 Complex: Magnetostructural Correlations in Two Polymorphs., Yoji Horii; Yuki Kanegae; Kiyonori Takahashi; Akira Fuyuhiro; Mariko Noguchi; Hal Suzuki; Motohiro Nakano, Two crystal polymorphs of Ni(cyclam)I2 (cyclam = 1,4,8,11-tetraazacyclotetradecane) were synthesized, and their magnetic properties were investigated. Temperature-dependent X-ray structural analysis and magnetic measurements revealed gradual spin transition in molecular-crystal polymorph trans-[Ni(cyclam)I2] (1a), whereas the zigzag-chain polymorph catena-[Ni(cyclam)(μ-I)]I (1b) did not show an obvious spin transition. The entropy difference between high- and low-spin states of 1a estimated by assuming the spin-equilibrium model is much smaller than those in typical iron(II)-based spin-crossover (SCO) complexes, suggesting that the normal mode softening is less remarkable in 1a. In this system, it is clearly evidenced that the interaction mode responsible to the spin equilibrium in octahedral nickel(II) complexes is highly anistropic, i.e., z-elongation and x,y-shortening of the coordination octahedron., 2020年04月20日, 59, 8, 5418, 5423, 研究論文（学術雑誌）, 国際誌, 10.1021/acs.inorgchem.9b03735
  • 査読あり, 英語, Chemistry (Weinheim an der Bergstrasse, Germany), Coexistence of Spin-Lattice Relaxation and Phonon-Bottleneck Processes in GdIII -Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions., Yoji Horii; Keiichi Katoh; Yuji Miyazaki; Marko Damjanović; Tetsu Sato; Liviu Ungur; Liviu F Chibotaru; Brian K Breedlove; Motohiro Nakano; Wolfgang Wernsdorfer; Masahiro Yamashita, Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+ -phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+ -Gd3+ interactions and the other does not. It was found that the Gd3+ -Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin-lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes., 2020年06月26日, 26, 36, 8076, 8082, 研究論文（学術雑誌）, 国際誌, 10.1002/chem.201905796
  • 査読あり, 英語, Chemistry (Weinheim an der Bergstrasse, Germany), Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy., Yoji Horii; Marko Damjanović; M R Ajayakumar; Keiichi Katoh; Yasutaka Kitagawa; Liviu Chibotaru; Liviu Ungur; Marta Mas-Torrent; Wolfgang Wernsdorfer; Brian K Breedlove; Markus Enders; Jaume Veciana; Masahiro Yamashita, Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic 1 H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charged quadruple and quintuple-decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single-molecule magnet properties, which are controlled by the multi-step redox induced structural changes., 2020年07月14日, 26, 39, 8621, 8630, 研究論文（学術雑誌）, 国際誌, 10.1002/chem.202001365
  • 査読あり, 英語, Chemical communications (Cambridge, England), Cocrystals of Li+ encapsulated fullerenes and Tb(iii) double-decker single molecule magnet in a quasi-kagome lattice., Hikaru Iwami; Junfei Xing; Ryo Nakanishi; Yoji Horii; Keiichi Katoh; Brian K Breedlove; Kazuhiko Kawachi; Yasuhiko Kasama; Eunsang Kwon; Masahiro Yamashita, Cocrystallization of a lithium ion encapsulated fullerene Li+@C60 with a terbium(iii) phthalocyaninato porphyrinato double-decker single-molecule magnet [Tb(Pc)(OEP)] is reported. The cocrystal, containing PF6- as a counter anion, packs in a quasi-kagome lattice, which leads to intermolecular ferromagnetic interactions as well as the modulation of the single-molecule magnet (SMM) properties., 2020年10月28日, 56, 84, 12785, 12788, 研究論文（学術雑誌）, 国際誌, 10.1039/d0cc04349d
  • 査読あり, その他, CHEMISTRY-A EUROPEAN JOURNAL, Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7 ',8,8 '-Tetracyano-p-quinodimethane, Ishikawa Ryuta; Ueno Shuya; Nifuku Shoei; Horii Yoji; Iguchi Hiroaki; Miyazaki Yuji; Nakano Motohiro; Hayami Shinya; Kumagai Shohei; Katoh Keiichi; Li Zhao-Yang; Yamashita Masahiro; Kawata Satoshi, The reaction of Fe(OAc)2 and Hbpypz with neutral TCNQ results in the formation of [Fe2(bpypz)2(TCNQ)2](TCNQ)2 (1), in which Hbpypz=3,5-bis(2-pyridyl)pyrazole and TCNQ=7,7′,8,8′-tetracyano-p-quinodimethane. Crystal packing of 1 with uncoordinated TCNQ and π–π stacking of bpypz− ligands produces an extended two-dimensional supramolecular coordination assembly. Temperature dependence of the dc magnetic susceptibility and heat capacity measurements indicate that 1 undergoes an abrupt spin crossover (SCO) with thermal spin transition temperatures of 339 and 337 K for the heating and cooling modes, respectively, resulting in a thermal hysteresis of 2 K. Remarkably, the temperature dependence of dc electrical transport exhibits a transition that coincides with thermal SCO, demonstrating the thermally induced magnetic and electrical bistability of 1, strongly correlating magnetism with electrical conductivity. This outstanding feature leads to thermally induced simultaneous switching of magnetism and electrical conductivity and a magnetoresistance effect., 2019年12月10日, 26, 6, 1278, 1285, 研究論文（学術雑誌）, 10.1002/chem.201903934
  • 査読あり, その他, CrystEngComm, Versatile coordination architectures of products generated by the in situ reaction of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear copper(ii) complex with tetracyanoethylene, Ryuta Ishikawa; Shunya Ueno; Yumi Hamatake; Yoji Horii; Yuji Miyazaki; Motohiro Nakano; Takeshi Noda; Mikoto Uematsu; Satoshi Kawata,

    Reaction of doubly bpypz− bridged Cu(ii) dinuclear complex and TCNE gave three versatile coordination assemblies with TCNE solvolysis derivatives, depending on reaction solvents.

    , 2019年02月13日, 21, 12, 1886, 1894, 研究論文（学術雑誌）, 10.1039/c9ce00036d
  • 査読あり, 英語, CHEMISTRY-A EUROPEAN JOURNAL, Detailed Analysis of the Crystal Structures and Magnetic Properties of a Dysprosium(III) Phthalocyaninato Sextuple-Decker Complex: Weak f-f Interactions Suppress Magnetic Relaxation, Horii Yoji; Katoh Keiichi; Sugimoto Kunihisa; Nakanishi Ryo; Breedlove Brian K; Yamashita Masahiro, In the research field of single-molecule magnets (SMMs), lanthanoid-lanthanoid interactions, so-called f-f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f-f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII -CdII -phthalocyaninato sextuple-decker complex (Dy2 Cd3 ) reveals that the intramolecular Dy-Dy length in Dy2 Cd3 is more than 13 Å, which is longer than the intermolecular Dy-Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole-dipole interactions are observed in Dy2 Cd3 . From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2 Cd3 is partially suppressed owing to the existence of very weak Dy-Dy interactions. Our results show that even very weak Dy-Dy interactions act as a dipolar bias, suppressing QTM., 2019年02月26日, 25, 12, 3098, 3104, 研究論文（学術雑誌）, 国際誌, 10.1002/chem.201805368
  • 査読あり, 英語, Inorganic Chemistry, Changing Single-Molecule Magnet Properties of a Windmill-Like Distorted Terbium(III) α-Butoxy-Substituted Phthalocyaninato Double-Decker Complex by Protonation/Deprotonation, Yoji Horii; Yusuke Horie; Keiichi Katoh; Brian K. Breedlove; Masahiro Yamashita, Synthesis, structures, and magnetic properties of α-butoxy-substituted phthalocyaninato double-decker complexes Tb(α-obPc)2 (1-) (α-obPc: dianion of 1,4,8,11,15,18,22,25-octa(n-butoxy)phthalocyaninato) with protonated (1H), deprotonated (1[HDBU]), and diprotonated forms (1H2+) are discussed. X-ray analysis was used to confirm the position of the proton in 1H, and it was revealed that the protonation induced asymmetric distortion in 1H. In contrast, 1[HDBU] was distorted in a highly symmetric windmill-like fashion. 1H is arranged in a slipped column array in the crystal packing, whereas 1[HDBU] is arranged in a one-dimensional fashion, in which the magnetic easy axes of 1[HDBU] lie along the same line. From direct-current (dc) magnetic measurements, ferromagnetic Tb-Tb interactions occur in both 1H and 1[HDBU], and magnetic hysteresis was observed. However, the area of the magnetic hysteresis in 1[HDBU] is larger than that in 1H, meaning that magnetic relaxation time (τ) is longer in 1[HDBU]. In addition, the results of alternating-current magnetic measurements in a zero dc magnetic field indicate that τ of 1[HDBU] is longer as compared to 1H. In other words, protonation/deprotonation affects not only the molecular structures and crystal packing but also the single-molecule magnet properties., 2018年01月16日, 57, 2, 565, 574, 研究論文（学術雑誌）, 10.1021/acs.inorgchem.7b02124
  • 査読あり, 英語, Chemistry - A European Journal, Supramolecular Approach for Enhancing Single-Molecule Magnet Properties of Terbium(III)-Phthalocyaninato Double-Decker Complexes with Crown Moieties, Yoji Horii; Shuhei Kishiue; Marko Damjanović; Keiichi Katoh; Brian K. Breedlove; Markus Enders; Masahiro Yamashita, A TbIII-phthalocyaninato double-decker ([1]0) single-molecule magnet (SMM) having four 15-crown-5 moieties in one of the ligands was synthesized, and its dimerization and magnetic properties were studied in an attempt to utilize the supramolecular aggregation for enhancing the SMM properties. Aggregation of [1]0 to form [12K4]4+ in the presence of K+ ions was studied by using UV/Vis-NIR absorption and NMR spectroscopies. For the magnetic measurements, [1]0 and [12K4]4+ were dispersed in poly(methyl methacrylate) (PMMA). UV/Vis-NIR absorption measurements on the PMMA dispersed samples were used to track the formation of [12K4]4+. Direct current (DC) magnetic susceptibility measurements revealed that there were ferromagnetic Tb–Tb interactions in [12K4]4+, whereas there was no indication of ferromagnetic interactions in [1]0. Upon the formation of [12K4]4+ from [1]0 and K+ ions, the temperature at which the magnetic hysteresis occurred increased from 7 to 15 K. In addition, the area of magnetic hysteresis became larger for [12K4]4+, meaning that SMM properties of [12K4]4+ are superior to those of [1]0. Alternating current (AC) magnetic measurements were used to confirm this observation. Magnetic relaxation times at 2 K increased 1000-fold upon dimerization of [1]0 to [12K4]4+, demonstrating the effectiveness of using K+ ions to induce dimer formation for the improvement of the SMM properties., 2018年03月20日, 24, 17, 4320, 4327, 研究論文（学術雑誌）, 10.1002/chem.201705378
  • 査読あり, 英語, CHEMICAL COMMUNICATIONS, Elongation of magnetic relaxation times in a single-molecule magnet through intermetallic interactions: a clamshell-type dinuclear terbium(III)-phthalocynaninato quadruple-decker complex, Yoji Horii; Keiichi Katoh; Brian K. Breedlove; Masahiro Yamashita, A clamshell-type terbium(III)-phthalocyaninato quadruple-decker complex was synthesized. Magnetic measurements revealed that Tb-Tb interactions caused an increase in the magnetic relaxation time and enhanced the SMM properties., 2017年07月10日, 53, 61, 8561, 8564, 研究論文（学術雑誌）, 10.1039/c7cc03553e
  • 査読あり, 英語, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Field-Induced Single-Ion Magnetism Based on Spin-Phonon Relaxation in a Distorted Octahedral High-Spin Cobalt(II) Complex, Ryuta Ishikawa; Yoji Horii; Ryo Nakanishi; Shunya Ueno; Brian K. Breedlove; Masahiro Yamashita; Satoshi Kawata, The six-coordinate mononuclear high-spin cobalt(II) complex [Co(bpy)(2)(ClAn)]EtOH (1; bpy = 2,2-bipyridine, ClAn(2-) = chloranilate) and its magnetically diluted analogue [Co0.1Zn0.9(bpy)(2)(ClAn)]EtOH (3), in which the Co-II centres of 1 are partially diluted with the magnetically inactive Zn-II centres of [Zn(bpy)(2)(ClAn)]EtOH (2) as a diamagnetic matrix, exhibited slow magnetic relaxation in applied direct-current (DC) magnetic fields. Fits of the DC magnetic data indicate that this new field-induced single-ion magnet possesses large positive axial and significant rhombic zero-field splittings. The results of temperature-dependent and DC-magnetic-field-dependent alternating-current magnetic measurements on 1 and 3, which is a field-induced single-ion magnet, agree with those from theoretical studies, and spin relaxation occurs through two-phonon Raman and direct spin-phonon bottleneck processes of Kramers ions., 2016年06月15日, 20, 3233, 3239, 研究論文（学術雑誌）, 10.1002/ejic.201600481
  • 査読あり, 英語, CHEMPHYSCHEM, How Ions Arrange in Solution: Detailed Insight from NMR Spectroscopy of Paramagnetic Ion Pairs, Marko Damjanovic; Takaumi Morita; Yoji Horii; Keiichi Katoh; Masahiro Yamashita; Markus Enders, Ion pairing between the paramagnetic anion [Tb(obPc)(2)](-) (obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), which has a very large magnetic anisotropy, with various diamagnetic counterions [P(Ph)(4)](+) (1a), [As(Ph)(4)](+) (1b), bis(triphenylphosphine) iminium ([PPN](+), 1c) and tetra-n-butylammonium ([TBA](+), 1d) was studied by means of H-1, C-13, N-14, and P-31 NMR spectroscopy in solution at various temperatures. The influence of the paramagnetic anion on the NMR spectroscopy properties of the diamagnetic cations allowed a detailed insight into the distances and relative orientations of the paired ions. Isotropic tumbling models for the description of the quaternary cations are inaccurate, particularly for [TBA](+) with its flexible butyl chains. The effects of temperature and concentration were also assessed. The advantage of this technique is that relatively large distances and the orientation between molecules or ions in solution can be studied., 2016年09月01日, 17, 21, 3423, 3429, 研究論文（学術雑誌）, 10.1002/cphc.201600804
  • 査読あり, 英語, INORGANIC CHEMISTRY, Weak Dy-III-Dy-III Interactions in Dy-III-Phthalocyaninato Multiple-Decker Single-Molecule Magnets Effectively Suppress Magnetic Relaxation, Yoji Horii; Keiichi Katoh; Goulven Cosquer; Brian K. Breedlove; Masahiro Yamashita, The Dy-III quintuple-decker complex DyCdCdDy and hetero quadruple-decker complex DyCdY were synthesized, and their magnetic properties were compared with those of the quadruple decker complex DyCdDy. Single-crystal X-ray analysis revealed that the coordination geometries around the Dy-III ions of DyCdCdDy, DyCdY, and DyCdDy were similar. dc (direct current) magnetic measurements indicated that DyCdCdDy had very weak ferromagnetic Dy-III-Dy-III interactions but DyCdY did not. From a comparison of the magnetic relaxation times (tau) of the three complexes, the tau values of DyCdCdDy and DyCdDy, which have weak Dy-III-Dy-III interactions, are longer than that of DyCdY. In other words, weak Dy-III-Dy-III interactions effectively suppress magnetic relaxation., 2016年11月, 55, 22, 11782, 11790, 研究論文（学術雑誌）, 10.1021/acs.inorgchem.6b01870
  • 査読あり, 英語, MATERIALS, Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation, Hikaru Iwami; Ryo Nakanishi; Yoji Horii; Keiichi Katoh; Brian K. Breedlove; Masahiro Yamashita, Lanthanoid metal-organic frameworks (Ln-MOFs) can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III) and Tb(III) ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4 0,4 ''-s-triazine-2,4,6-triyl-tribenzoic acid (H(3)TATB) as a ligand, two new Ln-MOFs, [Dy(TATB)(DMF)(2)] (1) and [Tb(TATB)(DMF)(2)] (2), were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets., 2017年01月20日, 10, 1, 研究論文（学術雑誌）, 10.3390/ma10010081
  • 査読あり, 英語, INORGANIC CHEMISTRY, alpha-Substituted Bis(octabutoxyphthalocyaninato)Terbium(III) Double-Decker Complexes: Preparation and Study of Protonation by NMR and DFT, Marko Damjanovic; Yusuke Horie; Takaumi Morita; Yoji Horii; Keiichi Katoh; Masahiro Yamashita; Markus Enders, Synthesis of the anionic, alpha-substituted, bis(phthalocyaninato)Tb-III complex [Tb(alpha-obPc)(2)](-) ([1](-)) (obPc = alpha-octabutoxyphthalocyaninato) leads to the isolation of its protonated form [1H](0). This complex was characterized by X-ray diffraction (XRD), mass spectroscopy (MS), infrared (IR) and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy. Crystal structure analysis did not allow localization of the additional proton, which is probably attached to the meso-N atom or isoindole-N atom of the phthalocyaninato ligand. [1H](0) can easily be deprotonated or protonated, giving the corresponding anionic and cationic complexes. The three compounds [1H](0), [1](-), and [1HH](+) were studied by a combination of paramagnetic NMR experiments (H-1, C-13, variable-temperature measurements, two-dimensional nuclear magnetic resonance and DFT calculations (done on Y-III analogues with octamethoxyphthalocyaninato ligands), for the purpose of elucidating the positions of the acidic protons and for understanding the structural changes of the coordination environment of the Tb ion induced by protonation., 2015年12月09日, 54, 24, 11986, 11992, 研究論文（学術雑誌）, 10.1021/acs.inorgchem.5b02391
  • 査読あり, 英語, INORGANIC CHEMISTRY, Effects of f-f Interactions on the Single-Molecule Magnet Properties of Terbium(III)-Phthalocyaninato Quintuple-Decker Complexes, Yoji Horii; Keiichi Katoh; Nobuhiro Yasuda; Brian K. Breedlove; Masahiro Yamashita, Single-molecule magnet (SMM) properties of terbium(III)-phthalocyaninato quintuple-decker complex TbCdCdTb were studied and were compared with those of other multiple-decker complexes (triple-decker: TbTb, quadruple-decker: TbCdTb) to elucidate the relationship between magnetic dipole interactions and SMM properties. From X-ray crystallography performed with synchrotron radiation, the Tb-III-Tb-III distance in TbCdCdTb was determined to be 9.883 angstrom. From alternating current magnetic studies on TbCdCdTb, the activation energy for spin reversal (Delta) increased with an increase in the direct current magnetic field (H-dc). This behavior is similar to that of TbCdTb, although the increase in Delta for TbCdTb is smaller. On the other hand, for TbTb, which has shortest Tb-III-Tb-III distance, Delta did not depend on H-dc, indicating that there is a correlation between SMM properties and the strength of the Tb-III-Tb-III interactions. By comparing the Zeeman diagrams for multiple-decker complexes, we found that the Tb-III-Tb-III interactions affected the magnetic field regions where quantum tunnelling of the magnetization was active. The results obtained from Zeeman diagrams are consistent with the results obtained from the magnetic studies., 2015年03月23日, 54, 7, 3297, 3305, 研究論文（学術雑誌）, 10.1021/ic502951t
  • 査読あり, 英語, DALTON TRANSACTIONS, Effect of f-f interactions on quantum tunnelling of the magnetization: mono- and dinuclear Dy(III) phthalocyaninato triple-decker single-molecule magnets with the same octacoordination environment, Keiichi Katoh; Rina Asano; Akira Miura; Yoji Horii; Takaumi Morita; Brian K. Breedlove; Masahiro Yamashita, The single-molecule magnet (SMM) behaviour of dinuclear Ln(III)-Pc triple-decker complexes (Dy(III)-Y(III): 1 and Dy(III)-Dy(III): 2) with the same octacoordination environment and slow magnetic relaxation behaviour were explained using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of dinuclear Dy(III)-Pc triple-decker type SMMs have never been discussed on the basis of the same octacoordination environment. Our results clearly show that the Dy(III) ion sites of 1 and 2 are equivalent, consistent with the crystal structure. 2 Exhibited ferromagnetic interaction between Dy(III) ions. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Dy(III) ions in the dinuclear systems. For both 1 and 2, quantum tunnelling of the magnetization (QTM) was observed. However, the magnetic relaxation time (tau) for 2 was one order of magnitude greater than that for 1, and single-component magnetic relaxation behaviour was explained. In other words, it is possible to use f-f interactions to increase tau by one order of magnitude., 2014年02月05日, 43, 21, 7716, 7725, 研究論文（学術雑誌）, 10.1039/c4dt00042k
  • 査読あり, 英語, DALTON TRANSACTIONS, Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes, Keiichi Katoh; Yoji Horii; Nobuhiro Yasuda; Wolfgang Wernsdorfer; Koshiro Toriumi; Brian K. Breedlove; Masahiro Yamashita, The SMM behaviour of dinuclear Ln(III)-Pc multiple-decker complexes (Ln = Tb3+ and Dy3+) with energy barriers and slow-relaxation behaviour were explained by using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of several dinuclear Ln(III)-Pc type SMMs have never been discussed on the basis of the crystal structure. For dinuclear Tb(III)-Pc complexes, a dual magnetic relaxation process was observed. The relaxation processes are due to the anisotropic centres. Our results clearly show that the two Tb3+ ion sites are equivalent and are consistent with the crystal structure. On the other hand, the mononuclear Tb(III)-Pc complex exhibited only a single magnetic relaxation process. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Tb3+ ions in the dinuclear systems. Furthermore, the SMM behaviour of dinuclear Dy(III)-Pc type SMMs with smaller energy barriers compared with that of Tb(III)-Pc and slow-relaxation behaviour was explained. Dinuclear Dy(III)-Pc SMMs exhibited single-component magnetic relaxation behaviour. The results indicate that the magnetic relaxation properties of dinuclear Ln(III)-Pc multiple-decker complexes are affected by the local molecular symmetry and are extremely sensitive to tiny distortions in the coordination geometry. In other words, the spatial arrangement of the Ln(3+) ions (f-f interactions) in the crystal is important. Our work shows that the SMM properties can be fine-tuned by introducing weak intermolecular magnetic interactions in a controlled SMM spatial arrangement., 2012年08月01日, 41, 44, 13582, 13600, 研究論文（学術雑誌）, 10.1039/c2dt31400b

MISC

  • その他, 熱測定, 単分子磁石の二量化に伴う量子トンネル効果の抑制, 堀井洋司; 堀井洋司, 2020年, 47, 3
  • 査読無し, 日本語, 月刊化学, 進化を続ける次世代型ナノ分子磁石-高温動作する単分子磁石を目指して!!, 堀井洋司; 加藤恵一; 山下正廣, 2014年, 1, 45, 50, 記事・総説・解説・論説等（その他）

講演・口頭発表等

  • 堀井 彩可, 国内, 日本化学会第103春季年会, 18員環ポリアミンを基盤とする12座かご型配位子を用いた単核希土類金属錯体の合成、構造と遅い磁化緩和の発現, ポスター発表, 2023年03月22日, 2023年03月25日, 日本語
  • 村井 文歌, 国内, 日本化学会第103春季年会, Gd(Ⅲ)単核錯体における遅い磁化緩和と集積化が磁気特性に及ぼす効果, ポスター発表, 2023年03月22日, 2023年03月25日, 日本語
  • 加藤日菜子, 国内, 日本化学会第103春季年会, 弾性を示すドデシル化ポルフィリン結晶の温度低下による軟化と力 学特性の連続制御, ポスター発表, 2023年03月22日, 2023年03月25日, 日本語
  • 荒谷郁実, 国内, 錯体化学会第72回討論会, フタロシアニン-ポルフィリンダブルデッカー型SMMから成る二次元ネットワーク構造の形成, 口頭発表（一般）, 2022年09月26日, 2022年09月28日, 日本語
  • 堀井洋司, 国内, 錯体化学会第72回討論会, Temperature-dependent elasticity of an elastic crystal composed of a porphyrin: suppression of curing upon cocrystallization with the metalloporphyrin, ポスター発表, 2022年09月26日, 2022年09月28日, 日本語
  • Yoji Horii, 国際, 2nd Asian Conference on Molecular Magnetism, Structural and Magnetic Study for Two-dimensional Metal-Organic Frameworks Composed of Single-Molecule Magnets, 口頭発表（一般）
  • Yoji Horii, 国際, The 73rd Yamada Conference, Two dimensional MOFs composed of SMMs, 口頭発表（招待・特別）, 英語
  • Yoji Horii, 国際, 8th Asian Conference on Coordination Chemistry, Tow-dimensional MOFs Composed of Single-Molecule Magnets, 口頭発表（一般）, 英語
  • 荒谷郁実, 国内, 日本化学会第１０２春季年会, フタロシアニン-ポルフィリンダブルデッカー型錯体から成る2次元ネットワーク構造の形成：フタロシアニン配位子のかさ高さと分子の配列様式の相関, ポスター発表, 2022年03月23日, 2022年03月26日, 日本語
  • 荒谷郁実, 国内, 錯体化学会第７１回討論会, 荒谷郁実、堀井洋司、高城大輔、梶原孝志, ポスター発表, 2021年09月16日, 2021年09月19日, 日本語
  • Yoji Horii, 国際, 17th International Conference on Molecule Based Magnets, Triplet biradical states of phthalocyaninato-terbium(III) multiple-decker complexes captured by paramagnetic NMR analyses, 口頭発表（一般）, 2021年06月14日, 2021年06月18日, 英語
  • Yoji Horii, 国際, The 1st Asian Conference on Molecular Magnetism, Triplet Biradical States in Oxidized Form of Phthalocyaninato-Lanthanoid(III) Multiple-Decker Complexes, 口頭発表（一般）, 2021年03月07日, 2021年03月10日, 英語

共同研究・競争的資金等の研究課題

  • 若手研究, 2021年04月01日, 2023年03月31日, 21K14645, 両親媒性配位子を用いた裏表を有する薄膜状配位高分子の運動機能性と磁気特性, 堀井 洋司, 日本学術振興会, 科学研究費助成事業 若手研究, 奈良女子大学, 4680000, 3600000, 1080000, rm:published_papers
    対象リソースIRI
  • 若手研究, 2018年04月01日, 2020年03月31日, 18K14242, 分子ローターの２次元高密度集積に伴うキラル反転相転移現象の検証, 堀井 洋司, 日本学術振興会, 科学研究費助成事業 若手研究, 4290000, 3300000, 990000, 本研究課題では、金属配位サイトを有する分子ローター錯体を合成し、金属イオンの存在下LB法を用いることで、分子ローター２次元集積体を合成した。AFMを用いた顕微鏡測定では、単分子膜に相当する厚さの膜状構造を確認しており、目的の構造体が生成していると思われた。また、薄膜の紫外可視吸収スペクトルでは、金属イオンとの反応前後において吸収スペクトルに明確な変化が見られず、集積後もローターの構造が保たれていることが示唆された。温度可変紫外可視吸収スペクトルにより、分子ローターの協奏的運動に伴う変化の観測を試みたが、現在までのところ相転移現象を示す証拠は得られていない。, url
    対象リソースIRI
  • 特別研究員奨励費, 2014年04月25日, 2017年03月31日, 14J02656, フタロシアニン多層積層型錯体を用いた分子デバイスの創出および新規物性の開拓, 堀井 洋司, 日本学術振興会, 科学研究費助成事業 特別研究員奨励費, 東北大学, 2800000, 2800000, 本年度は、フタロシアニン多層積層型錯体の構造と磁気物性の解明という観点から、１）フタロシアニン６層積層型錯体の結晶構造解明および２）フタロシアニン多層積層型錯体の酸化還元に伴う構造・磁気特性の変化の２つについて研究を行った。 １）これまでの研究より、フタロシアニン多層積層型錯体が単分子磁石として振る舞い、積層数を変化させることで分子内の磁気的な相互作用の強弱を制御できることが知られている。本テーマでは、これまでの報告されている中で最も分子内磁気相互作用の弱い６層積層型錯体の合成および結晶構造解明に成功し、６層錯体内の磁性原子は1.3 nm以上離れた距離にあることを明らかにした。従来の単分子磁石研究では、1nm以上離れた磁性イオン間の相互作用は無視できるほど小さいと考えられていた。しかしながら、６層錯体の磁化率測定を行ったところ、1.3 nm以上離れた磁性イオン間にも強磁性的な相互作用が働いており、単分子磁石特性に影響を与えうることが明らかとなった。本研究は単分子磁石設計にも応用できることから、分子磁性分野において一石を投じる結果である。 ２）フタロシアニン多層積層型錯体は拡張したπ共役系を有することから、多彩な酸化還元特性を示すことが明らかとなっている。これを単分子磁石特性と組み合わせることで、酸化還元に伴う磁気特性の制御が可能になると考えられる。以上の観点より、本テーマでは、フタロシアニン多層積層型錯体の高酸化状態における構造と磁気特性の解明を行った。結晶構造解析より、多層錯体は酸化に伴って分子を縦方向に圧縮するような変形を示すことを明らかにした。またこの構造変化に伴い、単分子磁石特性も大きく変化することを見出した。とくに４層・５層錯体では、これまでに報告されている中で最も多い５段階の磁気特性制御に成功した。

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