Hydrothermal Syntheses, Crystal Structures, and Properties of a Novel Class of 3,3‘,4,4‘-Benzophenone-tetracarboxylate (BPTC) Polymers

Abstract

Three novel BPTC complexes, (H(2)BPTC)(4,4'-H(2)bpy)H(2)O (1), [Cd(2)Cu(HBPTC)(2)(mu(2)-4,4'-bpy)(2)(4,4'-bpy)(2)(H(2)O)(2)](n) (2), and [Co(3)(HBPTC)(2)(mu(2)-4,4'-bpy)(3)(H(2)O)(4)](n).2nH(2)O (3) (BPTC = 3,3',4,4'-benzophenone-tetracarboxylate and bpy = bipyridine), were hydrothermally synthesized. Complex 1, which is obtained as a coproduct during the syntheses of complexes 2 and 3, features a 2-D layered strong hydrogen bonding network with 2-fold interpenetration. Complex 2 has an unusual 2-D double-layered motif, which is linked together by Cu atoms in a face-to-face manner. It exhibits nanosized channels filled by 4,4'-bpy ligands. Three six-coordinated Co atoms in 3 are interlinked by HBPTC ligands to form a 2-D grid structure, which is further sustained by rigid 4,4'-bpy ligands into a 3-D open framework similar to CdSO(4) with the BPTC moieties situated in the tunnels. The thermal stabilities of complexes 1-3 were examined. The photoluminescence properties of complexes 1-2 and temperature-dependent magnetic susceptibility for 3 were also studied.

Two isolated structural motifs in one crystal: One of which fills helical channels in another

“…Strong absorption bands between 1350 and 1600 cm −1 in the IR spectra of complex 1 can be assigned to the coordinated carboxylate groups. The sulfone characteristic bands are measured at around 1310 cm −1 , 1160 cm −1 , and 1080 cm −1 [13,14]. All these agree well with the result of X-ray single-crystal analyses.…”

Two novel Zn(II) coordination polymers based on a carboxylate functionalized imidazophenanthroline derivative ligand

“…457, 483 nm and 451, 498 nm upon excitation at 340 nm, respectively. The higher energy emission bands of 1 and 2 display slight blue-shifts of 6 and 12 nm relative to that of the free H 2 cpip ligand, which may be assigned to the intraligand transitions [12][13][14]. Notably, the lower energy emission bands were also observed at 483 nm for 1 and 498 nm for 2, which is indicative of intermolecular π…π stacking interaction.…”

A series of novel indium complexes derived from aromatic carboxylic acids: Hydrothermal syntheses, crystal structures, supramolecular networks and fluorescent properties

“…As an important multidentate O and N-donor ligand, 2,6-H 2 pydc (2,6-pyridine dicarboxylic acid), with a rigid 120°angle between the central pyridine ring and the two carboxylate groups, is a versatile ligand, and could provide various coordination modes [4]. H 4 bptc (3,3 ,4,4 -benzophenonetetracarboxylate), a flexible tetracarboxylic ligand is also worth to be introduced based on the following considerations: First, there are multiple bridging carboxylic groups, which may provide a variety of connection modes with metal centers [5]. Second, the relative flexibility around the ketone group can also generate different torsion angles between the two phenyl planes and the carboxylic groups, resulting in formation of different structures.…”