Structural diversity, photoluminescence and magnet properties of complexes based on a V-shaped polycarboxylate

摘要

The self-assembly of a V-shaped ligand 3,3′,4,4′- diphenylsulfonetetracarboxylate (dstc) and metal salts in the presence of a series of N-donor ligands yielded four new complexes, namely, [Cu _4(H_2dstc)_4(phen)_4]·12H _2O (1), {[Cu_2(dstc)(bpe)(H_2O) _2]·4H_2O}_n (2), [Cu_3(dstc) (bipy)(μ_2-OH)_2(H_2O)_2] _n (3), {[Cd_5(dstc)_2(bipy) _2(μ_3-OH)_2(H_2O) _4]·4H_2O}_n (4) (phen = 1,10-phenanthroline; bpe = 1,2-bis(4-pyridyl)ethene; bipy = 4,4′- bipyridine). All the complexes were structurally determined by single-crystal X-ray diffraction and characterized by elemental analyses, IR spectra, X-ray powder diffraction and TG analyses. Complex 1 is a discrete tetranuclear unit, which further assembles into a 3D supramolecular framework by intermolecular hydrogen bonding interactions. Complex 2 is composed of 2D 4~4 grid-like layers based on dinuclear copper units. Complex 3 features a rare 3D (6,8)-connected topological net consisting of trimetallic clusters. 12-connected pentanuclear cadmium clusters are observed in complex 4 and the resulting structure shows an uncommon (4,12)-connected topology. The structural differences among 1-4 demonstrate that the nature of the N-donor assistant ligands and metal ions can play critical roles in the formation and structures of the resulting complexes. Magnetic studies showed antiferromagnetic interactions for 1 and 3. In addition, the luminescent property of 4 was also studied.