Abstract
AbstractA series of supramolecular assemblies of types [Ag8(L)4](PF6)8 and [Ag4(L)2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H4‐L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H4‐L(PF6)4. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag4(L)2](PF6)4 or [Ag8(L)4](PF6)8 stoichiometry. The molecular structures of selected [Ag8(L)4](PF6)8 and [Ag4(L)2](PF6)4 assemblies were determined by X‐ray diffraction analyses. While H4‐L(PF6)4 does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties.
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