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

一维金属络合物的亲油性修饰提供了分子导线的自组装，这些分子导线表现出传统无机、聚合物或超分子化学所不具备的独特的溶液性质。在本研究中，我们主要研究了亲脂性线性金属络合物表面分子结合缝隙的形成，开发了以十二烷氧基丙基-1，2，4-三氮唑桥联的超分子Fe(II)络合物。它在固态下表现出迟缓的自旋交叉行为。等摩尔十二醇或十四醇与Fe(II)三氮唑配合物共浇铸得到了复合膜，其中醇分子通过van der Waals相互作用和离子氢键与配合物结合。有趣的是，在三元系薄膜的自旋交叉特性中出现了热滞效应。通过掺杂乙醇分子，低温(LS态)的片层结构转变为高温(HS态)的六方结构，如S…基本结构的更多结构转变导致了双稳态的产生。这项研究提供了第一个超分子控制热自旋交叉现象的例子。这一概念被进一步应用于Fe(II)三氮唑配合物与液晶的结合，证明了自旋交叉液晶凝胶的形成。为了光调节一维Fe(三氮唑)3配合物的形态，引入了偶氮苯发色团。紫外光照射黄色氯环己烷凝胶中的含偶氮苯的Fe(II)三氮唑络合物，使其流态化成橙色溶液。原子力显微镜观察到凝胶样品具有平行排列的纳米片状棒状结构。紫外光照射会导致分子线结构向波状结构转变。4.对有机凝胶的电化学控制进行了研究。循环伏安结果表明，线性三氮唑配合物在氯仿中表现出可逆的氧化还原行为。它们的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。从而形成了具有独特物理性质的配位链的刺激响应型分子导线。较少

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