Department of Organic Chemistry, Facultad de Ciencias, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza, CSIC, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Chemistry. 2010 Dec 27;16(48):14545-53. doi: 10.1002/chem.201001766.
Silver pyrazolates with columnar liquid-crystal phases that are stable at room temperature have been prepared by reaction of silver nitrate with 3,5-diarylpyrazolates. The complexes consist of open-chain oligomers, despite the fact that the most common structural type for homoleptic coinage metal pyrazolates is the trimeric metallacycle M(μ-pz). The special characteristics of silver in forming reversible metal-ligand bonds in solution, evidenced experimentally, leads to supramolecular organizations in which the silver cations promote self-organization of the nonmesomorphic pyrazolates into helical 1D polymers that exhibit columnar mesophases. The materials are readily soluble in common organic solvents and are liquid-crystalline over a broader temperature range than their gold counterparts, which are known to form discrete cyclic trinuclear species. Thin films of the silver complexes show luminescence at room temperature. The compounds described here are the first examples of luminescent metallomesogens formed by a main-chain coordination polymer.
已经通过硝酸银与 3,5-二芳基吡唑盐的反应制备了具有室温下稳定的柱状液晶相的银吡唑盐。尽管常见的同金属吡唑盐的结构类型是三聚体金属环[M(μ-pz)]3，但这些配合物由开链低聚物组成。实验证明，银在溶液中形成可逆的金属-配体键的特殊性质导致了超分子组织，其中银阳离子促进非介晶吡唑盐自组装成具有柱状介相的螺旋 1D 聚合物。这些材料在常见有机溶剂中易溶，并且具有比其金对应物更宽的温度范围的液晶相，已知金对应物形成离散的环状三核物种。银配合物的薄膜在室温下发出荧光。这里描述的化合物是由主链配位聚合物形成的发光金属介晶的第一个例子。
