Structural and spectroscopic data for the for a series of two-dimensional coordination polymers based on silver-pyridyl bonds

A series of new 2D coordination framework materials, based on Ag(I)-N bond formation, has been synthesised and structurally characterised by single crystal methods. Reactions between the poly-monodentate bridging ligand N,N'-((1r,4r)-cyclohexane-1,4-diyl)bis(1-(pyridin-3-yl)methanimine), L1, and silver salts yield compounds {[Ag(L1)(MeCN)](CF3SO3-)}n, 1, {[Ag(L1)(PF2O2-)]•H2O}n, 2 and {Ag2(L1)(Tosylate)2}n, 3. The frameworks of these materials exhibit two distinct net topologies, 36.46.53 (1 and 2) and 44.62 (3). In all cases, L1 ligands are found to be fully saturated in terms of metal-ion binding with both sets of pyridyl and imino N-atoms involved. Though in 1 and 2, crystallographically independent L1 moieties also display pyridyl-only binding. Either the anion (2 and 3), or solvent (1), act as terminal ligands to support inter-layer interactions in the solid-state. Despite the relatively labile nature of typical Ag(I)-N bonds, solvent-based exfoliation of crystals of 3 was shown to provide dispersions of large, µm2, flakes which readily deposit on oxide surfaces as single-molecule sheets, as revealed by AFM.

基于Ag(I)-N键合形成的一系列新型二维配位框架材料，经单晶方法合成并进行了结构表征。多齿桥连配体N,N'-((1r,4r)-环己烷-1,4-二基)双(1-(吡啶-3-基)亚甲基胺)，L1，与银盐之间的反应产生了化合物{[Ag(L1)(MeCN)](CF3SO3-)}n，1，{[Ag(L1)(PF2O2-)]•H2O}n，2和{Ag2(L1)(Tosylate)2}n，3。这些材料的框架表现出两种独特的网络拓扑结构，分别为36.46.53（1和2）和44.62（3）。在所有情况下，L1配体均被发现与金属离子结合充分饱和，涉及两组吡啶和亚氨基N原子。尽管在1和2中，晶体学上独立的L1部分也显示出仅吡啶的配位。要么是阴离子（2和3），要么是溶剂（1），在固态中作为端基配体以支持层间相互作用。尽管典型的Ag(I)-N键相对易解，但基于溶剂的晶体3的剥离实验表明，可以提供大尺寸、µm2的薄片分散体，这些薄片容易作为单分子层沉积在氧化物表面上，如原子力显微镜（AFM）所揭示。