Syntheses, crystal structures, and optical properties of five metal complexes constructed from a V-shaped thiophene-containing ligand and different dicarboxylate ligands.

Five new metal complexes, {[Ni(DIDP)(m-bdc)(H2O)]·5H2O}n (1), {[Zn(DIDP)(hfipbb)]·2DMA}n (2), {[Zn(DIDP)(4,4'-sdb)]·H2O}n (3), {[Co(DIDP)(p-bdc)]}n (4), and {[Co2(DIDP)(hfipbb)2]·H2O}n (5), have been synthesized by reactions of the corresponding metal ions with a V-shaped ligand 2,8-di(1H-imidazol-1-yl)dibenzothiophene (DIDP) and different aromatic dicarboxylic acids, namely isophthalic acid (m-H2bdc), terephthalic acid (p-H2bdc), 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), and 4,4'-sulfonyldicarboxylic acid (4,4'-H2sdb), respectively. The structures of the complexes were determined by X-ray single-crystal diffraction. Complex 1 is a 1D chain structure containing a one-dimensional channel along the a direction and is further extended via O-H···S hydrogen bonds and C-H···π stacking interactions into a 3D framework. Complex 2 exhibits a quasi 2D + 2D → 2D with parallel polycatenation of 2D (4, 4) nets. Complex 3 displays an unusual 2D + 2D → 3D parallel polycatenated framework based on a 2D 6(3)-hcb network. Complex 4 shows a 2D 4-connected {4(4)·6(2)}-sql network containing a one-dimensional channel along the b direction. The adjacent 2D networks are further extended via C-H···O hydrogen bonds into a 3D supramolecular framework. Complex 5 features a 2-fold interpenetrating 3D framework with a 6-connected {4(12)·6(3)} pcu topology. Furthermore, the thermal stability for 1-5 and luminescence properties of 2 and 3 have been studied. Moreover, the solid-state UV-visible spectroscopy experiments show that complexes 1-5 are all optical semiconductors with band gaps of 3.06, 3.18, 3.23, 2.98, and 3.17 eV, respectively.