Self-assembled supramolecular clusters based on phosphines and coinage metals: tetrahedra, helicates, and mesocates

An array of coordination-driven supramolecular metal-ligand clusters has been synthesized using polytopic phosphine ligands and coinage metals (Cu(+), Ag(+), Au(+)). Rigid 3-fold or 2-fold symmetric phosphine ligands have been prepared: 1,3,5-tris((4-(diphenylphosphino)ethynyl)phenyl)benzene) (tppepb, L(1)), 1,4-bis((diphenylphosphino)ethynyl)benzene (1,4-dppeb, L(2)), 1,3-bis((diphenylphosphino)ethynyl)benzene (1,3-dppeb, L(3)), 2,6-bis((diphenylphosphino)ethynyl)pyridine (2,6-dppep, L(4)), and 1,5-bis((diphenylphosphino)ethynyl)naphthalene (1,5-dppen, L(5)). Self-assembly of these ligands with coinage metals produces four different types of metal-ligand clusters, or in some cases coordination polymers, depending on number and relative geometry of the phosphine donor atoms. Supramolecular tetrahedral clusters of the formula M4(L(1))4I4 (M = Cu(+), Ag(+), Au(+)) were obtained with the tppepb ligand, encapsulating solvent molecules (either CH2Cl2 or DMF) as guests within the central cavity of the clusters. The ligands 1,3-dppeb (L(3)) and 2,6-dppep (L(4)) give achiral, triple-stranded, dinuclear mesocates with the formula M2(L)3I2 (M = Cu(+) or Au(+)). In contrast, the ligand 1,4-dppeb (L(2)) generates a triple-stranded, dinuclear helicate with Cu(+), but a coordination polymer with Au(+) (both with the empirical formula M2(L(2))3I2). Finally, coordination polymers were obtained from 1,5-dppen (L(5)) with Cu(+). The clusters have been fully characterized by single crystal X-ray crystallography, high-resolution mass spectrometry, (1)H NMR, and (31)P NMR.