1444820-03-4Relevant articles and documents
Self-assembled supramolecular clusters based on phosphines and coinage metals: Tetrahedra, helicates, and mesocates
Lim, Sang Ho,Cohen, Seth M.
, p. 7862 - 7872 (2013/08/23)
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, L1), 1,4-bis((diphenylphosphino)ethynyl) benzene (1,4-dppeb, L2), 1,3-bis((diphenylphosphino)ethynyl)benzene (1,3-dppeb, L3), 2,6-bis((diphenylphosphino)ethynyl)pyridine (2,6-dppep, L4), and 1,5-bis((diphenylphosphino)ethynyl)naphthalene (1,5-dppen, L5). 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 M 4(L1)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 (L4) give achiral, triple-stranded, dinuclear mesocates with the formula M2(L)3I2 (M = Cu+ or Au+). In contrast, the ligand 1,4-dppeb (L2) generates a triple-stranded, dinuclear helicate with Cu +, but a coordination polymer with Au+ (both with the empirical formula M2(L2)3I2). Finally, coordination polymers were obtained from 1,5-dppen (L5) with Cu+. The clusters have been fully characterized by single crystal X-ray crystallography, high-resolution mass spectrometry, 1H NMR, and 31P NMR.
