Coordination polymers based on dithiophosphato/dithiophosphonato nickel complexes and linear 1,4-di(3-pyridyl)buta-1,3-diyne ligand

The reactions between ligand 1,4-di(3-pyridyl)buta-1,3-diyne (L) and the differently P-substituted dithiophosphato [Ni((RO)2PS2)2] [R = Me (1), Et (2)] and dithiophosphonato [Ni((4-MeOC6H4)(RO)PS2)2] [R = Me (3), Et (4)] nickel complexes have been performed, and the solid state structures of the resulting coordination polymers [1·L]∞–[4·L]∞ investigated. L acts as spacer between the complex units driving the formation of zig-zag polymeric chains. Inter-chain interactions involving the P-substituents have been discussed and the different supramolecular 3D-constructs described. The L donor ability has been confirmed also by spectrophotometric determination of the formation constants of the species 1·2L, 2·2L and 1·2L, and by theoretical studies. The reactivity of the ligand 1,4-di(3-pyridyl)buta-1,3-diyne (L) towards differently P-substitued phosphorodithioato NiII complexes along with the equilibrium formation constants in solution, and the solid state structures of the resulting coordination polymers [1·L]∞, [2·L]∞, [3·L]∞, and [4·L]∞ are presented.