Hydrothermal synthesis, structures, and photoluminescent properties of benzenepentacarboxylate bridged networks incorporating zinc(II)-hydroxide clusters or zinc(II)-carboxylate layers.

The first coordination compounds of partially or wholly deprotonated benzenepentacarboxylic acid (H5L) were synthesized in the presence or absence of auxiliary 2,2'-bipyridyl (2,2'-bpy) and 1,10-phenanthroline (phen) ligands, and their crystal structures and photoluminescent properties were characterized. Their formulas are [Zn6(mu3-OH)2(L)2(H2O)6]n (1), [Zn5(mu3-OH)2(HL)2(2,2'-bpy)2]n (2), [Zn2(HL)(phen)2(H2O)2]n (3), and [Zn5(L)2(phen)4(H2O)3]n.2nH2O (4). Both 1 and 2 are three-dimensional (3D) zinc(II)-hydroxide cluster based coordination frameworks. 1 contains distorted chairlike hexanuclear Zn6(mu3-OH)2 cluster units as secondary building blocks. Each Zn6(mu3-OH)2 unit connects six others through the three-connected nodes of L5- ligands into a 3D rigid and condensed coordination network, whereas in 2, each pentanuclear Zn5(mu3-OH)2 unit connects the other six ones through the three-connected [HL]4- nodes into a 3D network in the simple cubic packing mode. 3 has two-dimensional (2D) Zn(II)-carboxylate supramolecular layers constructed from a one-dimensional (1D) coordination chain structure by hydrogen bonds of the water and mu5-[HL]4- bridges, whereas 4 has 2D coordination layers composed of Zn(II) and mu8-L5- bridges. The adjacent coordination assemblies in 3 and 4 are further extended by hydrogen bonds and pi...pi interactions into 3D supramolecular architectures. 1-4 are photoluminescent active materials, and their photofluorescent properties are closely related to their intrinsic structure arrangements.