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Formation of adaptable molecular clefts based on self-assembly of lipophilic Fe(II) triazole complexes and their spin crossover characteristics

基于亲脂性 Fe(II) 三唑配合物自组装的适应性分子裂缝的形成及其自旋交叉特性

基本信息

批准号：
16074211
负责人：
KIMIZUKA Nobuo
金额：
$ 9.92万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
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

项目摘要

Lipophilic modification of one-dimensional metal complexes provide self-assembly of molecular wires which exhibit unique solution properties not accessible from conventional inorganic, polymer or supramolecular chemistry. In this study, we focused on the creation of molecular binding clefts on the surface of lipophilic linear metal complexes.Supramolecular Fe(II) complexes bridged by dodecyloxypropyl-1, 2, 4-triazole was newly developed. It exhibited sluggish spin crossover behavior in the solid state. Co-casting of equimolar dodecanol or tetradecanol with the Fe(II)triazole complex afforded composite films in which alcohol molecules were bound to the complex via van der Waals interactions and ionic hydrogen bonding. Interestingly, thermal hysteresis was induced in the spin crossover characteristics of ternary cast films. By doping alcohol molecules, lamellar structures at lower temperatures (LS state) were converted to hexagonal structures at higher temperatures (HS state), and such s … More tructural transformation of basic structures caused generation of bistability. This study provides a first example of supramolecular control on the thermal spin crossover phenomena. This concept was further applied to the combination of Fe(II) triazole complexes and liquid crystals, which demonstrated the formation of spin crossover liquid crystalline gels.To photoregulate the morphology of 1D Fe(triazole)3 complexes, azobenzene chromophores were introduced. UV light irradiation of the azobenzene-containing Fe(II) triazole complex in a yellow chlorocyclohexane gel caused fluidization into an orange-colored solution. In AFM, parallel-aligned rod-like structures in nanosheets were observed for the gel samples. UV irradiation causes structural transformation to undulating molecular wire structures. 4 Finally, electrochemical control on organogels was investigated. Cyclic voltammetry indicates that linear Fe(II) triazole complex display reversible oxidation and reduction in chloroform. Their gel-to-sol transition characteristics are controllable based on oxidation/reduction of iron ions. Thus, stimuli-responsive molecular wires of coordination chains were created, which showed unique physical properties. Less

一维金属配合物的亲脂性修饰提供了分子线的自组装，表现出传统无机化学、聚合物化学或超分子化学无法获得的独特溶液性质。在本研究中，我们着重于在亲脂线性金属配合物表面产生分子结合裂缝。以十二烷基氧基丙基- 1,2,4 -三唑为桥接物的超分子Fe（II）配合物是新开发的。在固态中表现出缓慢的自旋交叉行为。等摩尔十二醇或十四醇与铁（II）三唑配合物共铸得到复合膜，其中醇分子通过范德华相互作用和离子氢键与配合物结合。有趣的是，在三元铸膜的自旋交叉特性中产生了热滞后。通过掺入醇分子，较低温度下（LS态）的片层结构在较高温度下（HS态）转变为六方结构，从而使基本结构发生更多的结构转变，从而产生双稳性。本研究提供了超分子控制热自旋交叉现象的第一个例子。将这一概念进一步应用于Fe（II）三唑配合物与液晶的结合，证明了自旋交叉液晶凝胶的形成。为了光调节1D铁（三唑）3配合物的形态，引入了偶氮苯发色团。紫外光照射含偶氮苯的铁（II）三唑配合物在黄色氯环己烷凝胶中引起流化成橙色溶液。在原子力显微镜下，凝胶样品在纳米片上观察到平行排列的棒状结构。紫外线照射使结构转变为波动的分子线状结构。最后，对有机凝胶的电化学控制进行了研究。循环伏安法表明，线性铁（II）三唑配合物在氯仿中表现出可逆的氧化还原。它们凝胶到溶胶的转变特性是基于铁离子的氧化/还原而可控的。从而形成了具有刺激响应性的配位链分子线，并表现出独特的物理性质。少