Role of Spacers and Substituents in the Self-Assembly Process: Syntheses and Characterization of Three Novel Silver(I)/Iodine Polymers

In our effort to systematically investigate the influences of ligand spacers and terminal groups on the Ag/I inorganic
framework with large organic cation SDAs (structure-directing agents) ([Et3N(CH2)4NEt3]2+, [Et3N(CH2)6NEt3]2+, and [Me3N(CH2)6NMe3]2+), three silver(I) coordination polymers, {[Et3N(CH2)4NEt3][Ag4I6]}n (1) {[Et3N(CH2)6NEt3][Ag5I7]}n (2), and {[Me3N(CH2)6NMe3][Ag4I6]}n (3), have been synthesized in polar organic solvent. 1−3 all consist of one-dimensional polymers that could be
described as edge-sharing AgI4 tetrahedrons. Electrostatic interactions between organic countercations and inorganic moieties are
presented and contribute to the crystal packing. The structural differences among 1−3 show the influences of the spacers and
substituents of SDAs on the linkage modes of AgI4 tetrahedrons. All compounds were further characterized with IR spectra, elemental
analysis, thermal measurements, fluorescence analysis, and optical limiting measurements.

本研究为系统探究配体间隔基与端基对以大体积有机阳离子结构导向剂（structure-directing agents，SDAs）（包括[Et3N(CH2)4NEt3]2+、[Et3N(CH2)6NEt3]2+与[Me3N(CH2)6NMe3]2+）构筑的银/碘无机骨架的影响，于极性有机溶剂中合成了三种银(I)配位聚合物：{[Et3N(CH2)4NEt3][Ag4I6]}n(1)、{[Et3N(CH2)6NEt3][Ag5I7]}n(2)与{[Me3N(CH2)6NMe3][Ag4I6]}n(3)。化合物1~3均由可被描述为共边AgI4四面体的一维聚合物链构成。有机抗衡阳离子与无机骨架间存在静电相互作用，该作用对晶体堆积具有贡献。1~3之间的结构差异体现了SDAs的间隔基与取代基对AgI4四面体连接方式的影响。所有化合物均通过红外光谱、元素分析、热分析、荧光分析及光限幅测试完成了进一步表征。