Synthesis, structures and NLO properties of five non-centrosymmetric coordination compounds from the copper(II)/dps system (dps = 4,4′-dipyridyl sulfide)

The formation, crystal structure and properties of five copper(II) coordination compounds with the angular ligand, 4,4′-dipyridyl sulfide (dps) are described, {[Cu3(μ-dps)4(μ-SO4)2(SO4)(H2O)5] · 10H2O}∞ (1 · 10H2O), [Cu(dps)4(H2O)2] · (ClO4)2 · H2O (2 · H2O), {[Cu(μ-dps)2(DMF)2](ClO4)2}∞ (3), {[Cu(μ-dps)2(H2O)2] · (NO3)2 · 2H2O}∞ (4 · 2H2O) and {[Cu3(μ-dps)6(DMF)2(H2O)4] · (NO3)6 · (DMF) · 6H2O}∞ (5 · DMF · 6H2O). The topological architectures of all these coordination compounds are strongly dependent on the counteranions, with the aid of guest solvents, and include a chiral 3D non-interpenetrated structure for 1, an acentric mononuclear structure for 2, acentric 2D undulating networks for 3 and 5, and a chiral 1D double-stranded chain for 4. In particular, all these acentric or chiral coordination architectures are generated from an achiral ligand as a building unit, and their second-order non-linear optical (NLO) properties are also studied in this paper.

Graphical abstractA series of acentric coordination frameworks constructed by Cu(II) and 4,4′-dipyridyl sulfide (dps) were synthesized. All these coordination architectures are generated from achiral building blocks without any chiral auxiliary. The influence of anion and solvent on the structural architecture is discussed. Their second-order NLO properties are also studied.Figure optionsDownload full-size imageDownload as PowerPoint slide