Supramolecular Coordination Cages Based on N-Heterocyclic Carbene-Gold(I) Ligands and Their Precursors: Self-Assembly, Structural Transformation and Guest-Binding Properties

The incorporation of functional groups into the cavity of discrete supramolecular coordination cages (SCCs) will bring unique functions and applications. Here, three dicarboxylate ligands (H₂ L1Cl, H₂ L2Cl and H₂ L3Cl) containing N-heterocyclic carbene (NHC) precursors as linkers were introduced to construct SCCs by combining with two C₃ -symmertic (CpZr)₃ (μ₃ -O)(μ₂ -OH)₃ clusters as three-connect vertices, resulted in a series of rugby-like V₂ E₃ (V=vertex, E=edge) type homoleptic cages (SCC-1, SCC-2 and SCC-3). However, V₄ E₆ -type tetrahedral cages (SCC-4 and SCC-5), incorporating six Au-NHC moieties, were obtained when the corresponding NHC-gold(I) functionalized ligands (H₂ L1^Au , H₂ L2^Au ) were applied. For the first time, we present a trackable CpZr-involved cage to cage conversion to generate a heteroleptic V₂ E₃ cage (SCC-6) from two homoleptic cages (SCC-2 and SCC-5) with different geometries of V₂ E₃ and V₄ E₆ . The heteroleptic assembly SCC-6 can also be formed upon a subcomponent displacement strategy. The structural transformation and reassembly processes were detected and monitored by ¹ H NMR spectroscopy and electrospray-ionization mass spectrometry. The formation of heteroleptic assembly was further supported by single crystal X-ray diffraction analysis. Moreover, homoleptic cage SCC-2 possesses a trigonal bipyramidal cationic cavity allowing the encapsulation of a series of sulfonate anionic guests.