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

Six d 10 metal metal-organic coordination polymers, {[Zn 2 (Htpim) 2 (tp) 2 ]·2H 2 O} n ( 1 ), {[Cd 3 (H 0.5 tpim) 4 (pa) 2 (H 2 O) 2 ]·5H 2 O} n ( 2 ), [Zn(Htpim) 2 (Htma)] n ( 3 ), {[Zn 4 (Htpim) 4 (ip) 4 ]·2H 2 O} n ( 4 ), [Cd(Htpim)(ca)] n ( 5 ), and {[Cd 4 (Htpim) 2 ( d -ca) 4 (H 2 O) 2 ]·5H 2 O} n ( 6 ) (Htpim = 2,4,5-tri(4-pyridyl)-imidazole, H 2 tp = terephthalic acid, H 2 pa = phthalic acid, H 3 tma = trimesic acid, H 2 ip = isophthalic acid, H 2 ca = racemic camphor acid, d -H 2 ca = 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 (5 3 )(5 4 ) 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.