Self-Assembly of Metal−Organic Coordination Polymers Constructed from a Versatile Multipyridyl Ligand: Diversity of Coordination Modes and Structures

Abstract

Six d10 metal metal-organic coordination polymers, {[Zn2(Htpim)2(tp)2]·2H2O}n (1), {[Cd3(H0.5tpim)4(pa)2(H2O)2]·5H2O}n (2), [Zn(Htpim)2(Htma)]n (3), {[Zn4(Htpim)4(ip)4]·2H2O}n (4), [Cd(Htpim)(ca)]n (5), and {[Cd4(Htpim)2(d-ca)4(H2O)2]·5H2O}n (6) (Htpim = 2,4,5-tri(4-pyridyl)-imidazole, H2tp = terephthalic acid, H2pa = phthalic acid, H3tma = trimesic acid, H2ip = isophthalic acid, H2ca = racemic camphor acid, d-H2ca = d-camphor acid), have been prepared and structurally characterized. In all complexes, the rigid ligand Htpim exhibits different coordination modes and leads to the formation of various architectures. Complex 1 shows a two-dimensional (2D) network with (6,3) topology, where hydrogen-bonding interactions further link these sheets to a three-dimensional (3D) supramolecular structure. Complex 2 exhibits a 2D layer with (53)(54) network topology. Complex 3 is a corrugated 2D layer with (4,4) topology, and the separated layers are connected through weak π−π stacking interactions to generate a 3D supramolecular architecture. Complex 4 is a rhombic 2D layer with (4,4) topology, and the 3D overlapped array is formed by hydrogen-bonding and π−π stacking interactions. A 3D diamondoid framework with 4-fold interpenetration is found in 5. Complex 6 contains a complicated 3D framework, and the vacancy is occupied by the guest water molecules. Their luminescent properties have been investigated in the solid state.