External Perturbation Responsible Multi-functional Metal Complexes

外部扰动负责的多功能金属配合物

• 批准号: 16205010
• 负责人: MATSUMOTO Naohide
• 金额: $ 28.04万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16205010/
• 关键词: spin crossover; hysteresis; extended structure; multi-step switching; iron complex; 双安定; スピン; 鉄錯体; 磁性; 構造; 光応答

Spin-crossover(SC)between the low-spin(LS)and high-spin(HS)states is the representative example of molecular bistability and can be utilized for information processing. The interaction between SC sites or the cooperativity governs the physical properties of SC such as the abruptness, multi-steps, and hysteresis. The rational molecular design is the important subject for SC materials. We report several families of SC compounds such as [Fe^<II>H_3L<Me>] Cl-X(X- = PF_6-, AsF_6-, SbF_6-, CF_3SO_3-). The complexes involved in one family were not only crystallized in the same monoclinic crystal system with the similar cell dimensions, but also assume the same space group P2_1/n at the HS state, P2_1 at the HS + LS state, and P2_1/n at the LS state. The general crystal structure consists of a 2D extended network structure constructed by NH... Cl- hydrogen bonds between the Cl- and the imidazole NH groups of three neighboring cations [Fe^<II>H_3L<Me>]^<2+>, while the anion X exists just as an isolated counter anion and occupies the space among the 2D sheets. Nevertheless the only counter anion is different in these complexes, a variety of SC behaviors, 1: a one-step SC of 2HS 〓 HS + LS, 2 : a two-step SC of 2HS HS + LS 〓2LS, 3 : a gradual one-step SC of HS 〓 LS, and 4 : a steep one-step SC of HS 〓 LS with hysteresis, has been observed. The molecular volumes of the counter anions are : V = 53.4 A^3 for BF_4-, V = 54.4 A^3 for C1O_4-, V = 73.0 A^3 for PF_6-, V = 78.5 A^3 for AsF_6-, V 88.7 A^3 for SbF_6-, V = 86.9 A^3 for CF_3S0_3-, and V = 94.4 A^3 for I_3-. These estimated relative sizes of the counter anions correlate fairly well with the SC behaviors. The present SC complexes supply the most useful model-compounds to experimentally and theoretically investigate the exact microscopic origin of the multi-step spin transition

低自旋（LS）和高自旋（HS）态之间的自旋交叉（SC）是分子双稳态的代表性例子，可用于信息处理。SC位点之间的相互作用或协同性决定了SC的物理性质，如非线性、多阶和滞后。合理的分子设计是超临界材料研究的重要课题。本文报道了几个系列的SC化合物，如[Fe^<II>H_3L<Me>] Cl-X（X- = PF_6-，AsF_6-，SbF_6-，CF_3SO_3-）。这三个配合物不仅属于同一个单斜晶系，晶胞尺寸相近，而且在HS态、HS + LS态和LS态分别具有相同的空间群P2_1/n、P2_1/n。一般晶体结构由NH +4构筑的二维扩展网络结构组成。Cl-与相邻三个阳离子[Fe^ H_3L ]^&lt;2+&gt;的咪唑NH基团之间存在Cl-氢键<II><Me>，而阴离子X仅作为孤立的抗衡阴离子存在，占据了二维片层之间的空间。然而，这些配合物中唯一的抗衡阴离子是不同的，各种SC行为，1：一个一步的SC的2 HS-HS + LS，2：一个两步的SC的2 HS HS + LS-2LS，3：一个渐进的一步SC的HS-LS，和4：一个陡峭的一步SC的HS-LS滞后，已被观察到。反阴离子的分子体积分别为：BF_4-V = 53.4 A^3，ClO_4-V = 54.4 A^3，PF_6-V = 73.0 A^3，AsF_6-V = 78.5 A^3，SbF_6-V = 88.7 A^3，CF_3SO_3-V = 86.9 A^3，I_3-V = 94.4 A^3。这些估计的抗衡阴离子的相对尺寸与SC行为相当相关。目前的SC配合物提供了最有用的模型化合物的实验和理论研究的确切微观起源的多步自旋转变

项目成果

Chiral Ferromagnetic Chain of Copper(II)-Gadolinium(III)Complex

铜(II)-钆(III)络合物的手性铁磁链

• 发表时间: 2009
• 期刊: Chemistry Letters 38
• 作者: Takefumi Hamamatsu;Naohide matsumoto;et al.
• 通讯作者: et al.

One-Dimensional Polynuclear Spin Crossover Iron(III) Complexes Bridged by 1,4-Bis-imidazoylbutane

1,4-双咪唑基丁烷桥接的一维多核自旋交叉铁(III)配合物

• 发表时间: 2006
• 作者: S.;Imatomi;R.;Kitashima;T.;Hamamatsu;Y.;Ogawa;N.;Matsumoto
• 通讯作者: Matsumoto

Tetranuclear 3d-4f single molecule magnets : [Cu^<II>LDy^<III>(hfac)_2]_2

四核3d-4f单分子磁体：[Cu^<II>LDy^<III>(hfac)_2]_2

• 发表时间: 2005
• 作者: Naohide;Matsumoto;Shutaro;Osa;Jerzy;Mrozinski
• 通讯作者: Mrozinski

Mossbauer Spectroscopic Studies of Mixed-Valence Spin Crossover Complexes

混合价自旋交叉配合物的穆斯堡尔谱研究

• 发表时间: 2004
• 作者: S.;Iijima;F.;Mizutani;O.;Niwa;N.;Matsumoto;Y.;Sunatsuki;M.;Kojima
• 通讯作者: Kojima

Structural-electronic correlation in the first-order phase transition of [FeH_2L^<2-Me>](ClO_4)_2(H_2L^2-Me=Bis[((2-methylimidazol-4yl)methylidene)-3-aminopropyl]ethylenediamine)

[FeH_2L^<2-Me>](ClO_4)_2(H_2L^2-Me=Bis[((2-甲基咪唑-4基)亚甲基)-3-氨丙基]乙二胺一级相变中的结构-电子关联

• 发表时间: 2006
• 期刊: Iorganic Chemistry 45
• 作者: Brefuel;N.;Imatomi;S.;Torigoe;H.;Hagiwara;H.;Shova;S.;Meunier;J.-F.;Bonhommeau;S.;Matsumoto;N.
• 通讯作者: N.