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

• 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

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] 家族的一系列双核二铁 (II) 配合物的光磁性质，其中 bpypz = 3,5-双 (吡啶-2-基)吡唑盐且 X = 4-Mepy (1)、py (3)、3-Mepy (4)、3-Cipy (5) 和 3-Brpy (6) 已被研究。反射率 T(LIESST) 温度以及动力学衰减。所有这些配合物都表现出以 100-150 K 为中心的完整热自旋跃迁，并在低温下经历光致激发自旋态捕获 (LIESST) 效应。每种化合物的光致高自旋态的 T(LIESST) 弛豫温度已被确定。对于所有这些化合物，低温下的 T(LIESST) 曲线都接近于以 HS 电子构型中的两个铁 (II) 金属离子为特征的 [{Fe (NCS)(3,5-Me_2py)}_2(bpypz)_2] (7) 配合物的反铁磁响应，给出了定量 LS-LS → HS-HS 光转换过程的一些证据。根据协同性的性质，动力学采用拉伸指数、简单指数或 S 形模型进行处理。有趣的是，这一系列双核配合物遵循先前提出的 T(LIESST) 与其热自旋跃迁温度 T_<v2> 之间的线性关系： T(LIESST) = T_0-0.3 T1_<v2> 这些化合物的 To 等于 100 K。基于此，并通过使用热自旋跃迁与哈米特常数之间发现的经验线性关系，配合物 7 的 HS-HS 性质有 被理解为 T(LIESST) 高于 T_<v2> 的物理不可能性的反映。通过施加静水压力连续检查了7上的热自旋交叉现象的附近。

项目成果

Synthesis and magneto-optical properties of a series of bisβ-diketonato) Co (II) complexes with imino nitroxide radical chelate

一系列双β-二酮Co(II)与亚氨基氮氧自由基螯合物的合成和磁光性质

• 发表时间: 2007
• 期刊: Polyhedron 26
• 作者: Takuzo Komiyama;Yutaka Takaguc;T. Ishida
• 通讯作者: T. Ishida

Synthesis and magneto-optical properties of a series of bis(β-diketonato) Co(II) complexes with imino nitroxide radical chelate

一系列双(β-二酮)Co(II)亚氨基氮氧自由基螯合物配合物的合成及磁光性质

• 发表时间: 2007
• 期刊: Polyhedron (in press)
• 作者: Komiyama;Takuzo; Takaguchi;Yutaka; Tsuboi;Sadao;T.Ishida
• 通讯作者: T.Ishida

A Novel Ruthenium-Quinonoid Complex. Structural, Spectroscopic, and Electrochemical Characterizations of Ruthenium(II)Bis(2,2'-bipyridine)Chloranilate

一种新型钌-醌类复合物。

• 发表时间: 2007
• 期刊: Chem. Lett. 36
• 作者: Komiyama;Takuzo; Takaguchi;Yutaka; Tsuboi;Sadao;R. Ishikawa
• 通讯作者: R. Ishikawa

Stepwise guest adsorption with large hysteresis in a coordination polymer {[Cu(bhnq)(THF)2](THF)}n constructed from a flexible hingelike ligand.

• DOI: 10.1021/ic060046e
• 发表时间: 2006-04
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Koichi Yamada;Hirokazu Tanaka;Sadahiro Yagishita;K. Adachi;T. Uemura;S. Kitagawa;S. Kawata

An [Fe_3O]^<4+> Core Wrapped by Two [FeL_3] Units

由两个 [FeL_3] 单元包裹的 [Fe_3O]^<4 > 核心

• 发表时间: 2006
• 期刊: Angew. Chem. Int. Ed. 45・33
• 作者: Barkakaty;Balaka; Takaguchi;Yutaka; Tsuboi;Sadao,;K.Yoneda
• 通讯作者: K.Yoneda