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The self-assembly of mechanoluminochromic polynuclear gold­(I) complexes has attracted more and more attention in the field of supramolecular gold­(I) chemistry. In this work, we adopted a stepwise self-assembly strategy to precisely synthesize two polynuclear gold­(I) supramolecular clusters. Through cooperative AuI···AuI and Au–N interactions, the gold­(I) clusters 1 +•BF4 – and 2 4+•4BF4 – with Au4 and Au16 cores, respectively, were successfully constructed. In these supramolecular clusters, (dppm)­Au2Cl2 coordination motifs and trithiocyanuric linkers were stepwise assembled via sequential thiolate–chloride/phosphine coordination substitution and Au–S/Au–N coordination bond rearrangement. Two well-defined gold­(I) supramolecular clusters displayed intense emission both in the solid state and in solution. Furthermore, the ladder-shaped cluster 2 4+•4BF4 – exhibited reversible mechanochromic luminescence behavior in the solid state as well as aggregation-caused redshifted emission in solution. Upon mechanical grinding, the emission of the cluster 2 4+•4BF4 – changed from yellow at 582 nm to red at 612 nm. The initial emission could be fully recovered by treatment with acetonitrile.

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The regulated self-assembly of adjustable-structure cuprous iodide cluster-based supramolecules still presents a significant challenge. In this study, we adopt two flexible quinoline-based ligands (L 1 and L 2 ), which can form a C 3-symmetric cavity through conformation vibration. By the employment of a conformation-adaptive self-assembly strategy, a high yield of two host–guest-encapsulated cuprous iodide cluster-based supramolecular architectures [(Cu3I3)L 1–2 ] (C1 and C2) is precisely synthesized. The trapped Cu3I3 cyclic core is supported by organic ligands via Cu–N and Cu–O synergistic coordination bonds, associated with metal–metal bonding interactions. These neutral supramolecular clusters, C1 and C2, exhibit red emissions in the solid state and blue emissions in the solution. Additionally, such trinuclear clusters demonstrate high photocatalytic activity with azide–alkyne cycloaddition reactions in water.