Construction of novel spin-crossover systems by nano space control of assemblies

通过组件的纳米空间控制构建新型自旋交叉系统

基本信息

批准号：
18550055
负责人：
KAWATA Satoshi
金额：
$ 2.57万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550055/
关键词：
Spin Crossover Binuclear Complex Iron(II)LIESST ヘリケート

项目摘要

Photomagnetic properties of a series of binuclear diiron(II) complexes belonging to the [{Fe(NCS)(py-X)}_2(bpypz)_2] family with bpypz = 3,5-bis (pyridine-2-yl)pyazolate and X = 4-Mepy (1), py (3), 3-Mepy (4), 3-Cipy (5) and 3-Brpy (6) have been investigated. The reflectivity T(LIESST) temperatures as well as the kinetic decays. All these complexes display a complete thermal spin transition centred between 100-150 K, and undergo the light-induced excited spin state trapping (LIESST) effect at low temperatures. The T(LIESST) relaxation temperature of the photoinduced high-spin state for each compound has been determined. For all of them the T(LIESST) curves at low temperature have been found close to antiferromagnetic response of the [{Fe (NCS)(3,5-Me_2py)}_2(bpypz)_2] (7) complex characterized by two iron(II) metal ions in HS electronic configuration, giving some evidences of a quantitative LS-LS → HS-HS photoconversion process. Depending on the nature of the cooperativity, kinetics have been treated with stretched exponential, simply exponential or sigmoidal model. Interestingly this series of dinuclear complexes follow a previously proposed linear relation between T(LIESST) and their thermal spin-transition temperatures T_<v2>: T(LIESST) = T_0-0.3 T1_<v2> To for these compounds is equal to 100 K. Based on that and by using the empirical linear relation found between the thermal spin transition and the Hammett constant, the HS-HS properties of complex 7 have been understood as a reflect of the physical impossibility that the T(LIESST) was higher than T_<v2>. The close vicinity of the thermal spin crossover phenomenon on 7 has been successively checked by applying hydrostatic pressure.

属于[{{fe（ncs）（py-x）} _ 2（bpypz）_2]的一系列双核二龙（II）复合物的光磁特性，具有BPYPZ = 3,5-5-双基（吡啶 - 2-基）吡唑酸酯（吡啶 - 2-基）和x = 4-mepy（py）（3-c），3-c = 4-mepy（3-c），3-c。已经研究了3毛（6）。反射率t（Liesst）温度以及动力学衰减。所有这些配合物显示出以100-150 K之间为中心的完整的热自旋转变，并在低温下经历了光引起的激发自旋陷阱（LIESST）效应。已经确定了每种化合物的光诱导的高旋转状态的T（Liesst）松弛温度。对于所有这些，都发现在低温下的t（Liesst）曲线接近[{fe（ncs）（3,5-me_2py）} _ 2（BPYPZ）_2]（7）复合物在HS电子构型中以HS电子配置中的两个铁（II）金属的特征，从而给予某些数量的photiit lss-hs-hs-hs的抗铁磁反应。根据协调的性质，动力学已通过拉伸指数，指数级或乙状结肠模型处理。 Interestingly this series of dinuclear complexes follow a previously proposed linear relation between T(LIESST) and their thermal spin-transition temperatures T_<v2>: T(LIESST) = T_0-0.3 T1_<v2> To for these compounds is equal to 100 K. Based on that and by using the empirical linear relation found between the thermal spin transition and the Hammett constant, the HS-HS properties of complex 7 have被理解为反映了t（Liesst）高于t_ <v2>的物理不可能。通过施加静水压力，已成功检查了7点热自旋跨界现象的近距离。