In situ amination and side group effect of multifunctional heterocyclic thione ligand toward discrete and polymeric cluster constructions.

Three metal complexes [Cu(I)6(atdm)6] (1), [Cu(I)(Hatd)(H2atd)] (2) and [H3O][Co(II)4Co(III)2Cl3(atd)6]·H2O (3) [atdm = 4-dimethylamino-6-anilino-1,3,5-triazine-2-thiolate, H2atd = 6-anilino-1,3,5-triazine-2,4-dithiol, atdH2 = 6-anilino-1,3,5-triazine-2,4(1H,3H)-dithione] have been solvothermally synthesized. The luminescent complexes 1 and 2 provide remarkable structural diversity depending on different reaction solutions. Complex 1 consists of a discrete pseudohexagonal prismatic [Cu6S6] core that can be described as two stacked, chair-shaped [Cu3S3] rings bound together by the C-N bridges of the atdm ligands, in which the atdm ligand was generated via in situ amination of H2atd in the presence of DMF solution. Whereas complex 2 is a 2D (4,4) net based on single node Cu(I) ions crystallized in acetonitrile, in which H2atd ligands exist in the thione form atdH2 and the partially deprotonated form atdH. Complex 3 has a two-fold interpenetrated (10,3)-a topological network based on unprecedented cobalt-centered trigonal-bipyramidal [Co6(atd)6] building blocks, linked by Cl(-) double-bridges and showing oriented effects of aniline side groups. IR spectra, elemental analyses and XRD analyses confirmed the phase-purities of the as-synthesized complexes. The photoluminescence properties of 1 and 2 in the solid state and the magnetic properties of 3 are investigated. A discussion of the crystal structures, as well as the coordination properties of the multifunctional sulfur-containing ligands upon different geometries of the central units, is also provided.