Abstract
The post‐assembly modification (PAM) of metallosupramolecular assemblies plays an important role in obtaining diverse architectures and expanding new functions. In this work, the trinuclear organometallic assemblies [Ag3(L)2](PF6)3 (L = 1a–c) were generated from the corresponding internal olefin‐bridged trisimidazolium, trisbenzoimidazolium, and trisimidazo[1,5‐ɑ]pyridinium salts H3‐L(PF6)3 (L = 1a–c) with Ag2O through coordination‐driven self‐assembly. Subsequently, complexes [Ag3(L)2](PF6)3 (L = 1a, 1b) were converted into corresponding gold(I) complexes [AuI3(L)2](PF6)3 (L = 1a, 1b) by transmetalation reaction. The oxidation addition of the gold(I) complexes [AuI3(L)2](PF6)3 (L = 1a, 1b) were carried out using iodine as an oxidant to give gold(III) complexes [AuIII3(L)2I6](PF6)3 (L = 1a, 1b). Irradiation of complexes [Ag3(L)2](PF6)3 (L = 1a, 1b) in solution leaded to structural transform into the corresponding cyclobutane‐bridged complexes [Ag3(L′)](PF6)3 (L′ = 2a, 2b) with quantitative yields.
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