Study on Spin Crossover Complexes with Multi-dimensional Network Structure

多维网络结构的自旋交叉配合物研究

• 批准号: 14340209
• 负责人: MATSUMOTO Naohide
• 金额: $ 9.47万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340209/
• 关键词: Spin Crossover; Photo-induction; Hydrogen Bonds; Supramolecules; Proton; Mixed-Valence; Chiral Assembly; 分子デバイス; キラリティ; 多次元構造; 光デバイス

The phenomenon of spin crossover between the low-spin (LS) and high-spin (HS) states, which is induced by external perturbation such as temperature, pressure, and light irradiation, is one of the most spectacular examples of molecular bistability. The bistability of the spin crossover behavior is governed by the cooperative interaction between the spin crossover sites. Therefore, a novel ligand system, which can provide not only spin crossover but also can produce interaction between spin crossover sites, is now required. We synthesized here a new family of spin crossover complexes with the various oxidation states and the various degree of the deprotonation at the imidazole moiety, [Fe^<II>H_3L^<Me>](NO_3)_2・1.5H_2O (1), [Fe^<III>L^<Me>]・3.5H_2O (2), [Fe^<II>H_3L^<Me>][Fe^<II>L^<Me>]NO_3 (3), and [Fe^<II>H_3L^<Me>][Fe^<III>L^<Me>](NO_3)_2 (4). The crystal structural analysis of 3 showed an unprecedented 2D homochiral assembly structure constructed by the imidazole-imidazolate hydrogen bonds between [Fe^<II>H_3L]^<2+> and [Fe^<II>L]-components with the same chirality. Compounds 3 and 4 also present the LIESST (light induced excited spin state trapping) effect. More surprisingly, a series of compounds involving the multi-functional compound exhibiting such complicated electronic structures and bulk optical activity is obtained by the adjustment of pH and by a one-pot assembly reaction of a programmed single molecule.

由温度、压力和光照射等外部扰动引起的低自旋（LS）态和高自旋（HS）态之间的自旋交叉现象是分子双稳态最引人注目的例子之一。自旋交叉行为的双稳定性由自旋交叉位点之间的协作相互作用控制。因此，现在需要一种新型配体系统，它不仅可以提供自旋交叉，而且可以在自旋交叉位点之间产生相互作用。我们在这里合成了一个新的自旋交叉配合物家族，其咪唑部分具有不同的氧化态和不同的去质子化程度，[Fe^<II>H_3L^<Me>](NO_3)_2·1.5H_2O (1)、[Fe^<III>L^<Me>]·3.5H_2O (2)， [Fe^<II>H_3L^<Me>][Fe^<II>L^<Me>]NO_3 (3) 和 [Fe^<II>H_3L^<Me>][Fe^<III>L^<Me>](NO_3)_2 (4)。 3的晶体结构分析表明，由具有相同手性的[Fe^<II>H_3L]^<2+>和[Fe^<II>L]-组分之间的咪唑-咪唑氢键构建了前所未有的二维纯手性组装结构。化合物 3 和 4 还呈现 LIESST（光诱导激发自旋态捕获）效应。更令人惊讶的是，通过调节pH值和通过编程的单分子的一锅组装反应获得了一系列涉及表现出如此复杂的电子结构和本体光学活性的多功能化合物的化合物。

项目成果

Ohta, Y., 他5名: "Spin crossover in a supramolecular Fe(II)-Fe(III) system"Material Science-Poland. 21(2). 191-198 (2003)

Ohta, Y. 和其他 5 人：“超分子 Fe(II)-Fe(III) 系统中的自旋交叉”Material Science-Poland 21(2) (2003)。

Sunatsuki Y., 他10名: "An unprecedented homochiral mixed-valence spin-crossover compound"Angewandte Chemie International Edition. 42. 1614-1618 (2003)

Sunatsuki Y. 和其他 10 人：“一种前所未有的同手性混合价自旋交叉化合物”Angewandte Chemie 国际版 42. 1614-1618 (2003)。

Osa S, Sunatsuki Y, Yamamoto Y, Nakamura M, Shimamoto T, Matsumoto N, Re N.: "Synthesis and magnetic properties of heterometalcyclic tetranuclear complexes [(CuML(hfac)]_2 (M = Zn, Cu, Ni, Co, Fe, Mn ; H_3L=1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybe

Osa S、Sunatsuki Y、Yamamoto Y、Nakamura M、Shimamoto T、Matsumoto N、Re N.：“异金属环四核配合物 [(CuML(hfac)]_2 (M = Zn、Cu、Ni、Co、

Ohta, Y., 他5名: "Spin crossover in a supramolecular Fe(II)-Fe(III) system"Material Science-Poland. 21. 191-198 (2003)

Ohta, Y. 和其他 5 人：“超分子 Fe(II)-Fe(III) 系统中的自旋交叉”Material Science-Poland 21. 191-198 (2003)

Ikuta Y., 他10名: "A new family of spin crossover complexes with a tripod ligand"Inorganic Chemistry. 42. 7001-7017 (2003)

Ikuta Y. 和其他 10 人：“具有三脚配体的自旋交叉配合物的新家族”无机化学 42. 7001-7017 (2003)。