Nickel(II) complexes based on dithiolate-polyamine binary ligand systems: crystal structures, hirshfeld surface analysis, theoretical study, and catalytic activity study on photocatalytic hydrogen generation.

To ascertain the influence of binary ligand systems [1,1-dicyanoethylene-2,2-dithiolate (i-mnt-2) and polyamine {tetraen = tris(2-aminoethyl)amine, tren = diethylene triamine and opda = o-phenylenediamine}] on the coordination modes of the Ni(ii) metal center and resulting supramolecular architectures, a series of nickel(ii) thiolate complexes [Ni(tetraen)(i-mnt)](DMSO) (1), [Ni2(tren)2(i-mnt)2] (2), and [Ni2(i-mnt)2(opda)2]n (3) have been synthesized in high yield in one step in water and structurally characterized by single crystal X-ray crystallography and spectroscopic techniques. X-ray diffraction studies disclose the diverse i-mnt-2 coordination to the Ni+2 center in the presence of active polyamine ligands, forming a slightly distorted octahedral geometry (NiN4S2) in 1, square planar (NiS4) and distorted octahedral geometries (NiN6) in the bimetallic co-crystallized aggregate of cationic [Ni(tren)2]+2 and anionic [Ni(i-mnt)2]-2 in 2, and a one dimensional (1D) polymeric chain along the [100] axis in 3, having consecutive square planar (NiS4) and octahedral (NiN6) coordination kernels. The N-HO, N-HS, N-HN, N-HS, N-HN, and N-HO type hydrogen bonds stabilize the supramolecular assemblies in 1, 2, and 3 respectively imparting interesting graph-set-motifs.