Mole-Ratio-Dependent Supramolecular Isomerism in Ag(I) Coordination Networks

Abstract

Three regioisomers (o-L,m-L, andp-L) of bis(cyanobenzyl)sulfide were employed to examine the effect of ligand isomers on the networking assembly. In the reaction ofm-Lwith silver(I) nitrate, supramolecular isomers1and2of stoichiometry [Ag2(m-L)(NO3)2]n, each comprising a 2D polymeric network were obtained on varying the mole-ratio of the reactant (see the below scheme). Notably, the overall structural motifs of1and2are mainly due to the conformational differences of the tridentatem-L: `S-shaped' in isomer1and `V-shaped' in isomer2. Under identical reaction conditions, the ligand isomerso-Landp-Lyield a loop-chain type 1D coordination polymer [Ag(o-L)NO3]n(3) and a multichannel 3D framework structure [Ag2(p-L)(NO3)2]n(4), respectively. The formation of these products shows no mole-ratio dependency.1Among the ligand isomer,p-Lshowed the anion-dependent complexes5-7with different topologies in the reactions of silver(I) salts (X = ClO4-, PF6-, or CF3CO2-). AgClO4afforded a double-stranded 1D polymer of type [Ag(p-L)(ClO4)]n(5). Meanwhile, treatment of AgPF6and AgCF3CO2afforded a 2-fold interpenetrated 3D coordination polymer {[Ag3(p-L)4](PF6)3·4CH2Cl2}n(6) and a multichannel 3D network [Ag2(p-L)(CF3CO3)2]n(7), respectively.