A series of silver coordination complexes (CCs) have been synthesized through self-assembly of five pyridine-substituted tetraphenylethylene stereoisomer ligands with silver ions (named , , , , and ). These silver CCs show distinct topologies including beaded chain frameworks, linear structures, and discrete metallacycles. The single-crystal analysis results reveal the critical role of the space distribution of the coordination site and stereoisomer ligands in controlling the silver CCs' geometry configuration and modulating the optical properties. Luminescent investigations revealed that , , , and possess obvious mechanocharomic behaviors, which can be achieved several reversible cycles through repeated grinding and methanol soaking processes. However, the showed tenacious stability toward mechanical grinding and temperature. Thus, these silver CCs provide a good platform to investigate the influence of the space distribution of the coordination site of ligands on their geometry and mechanocharomic properties.
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