Coordination Polymers of Copper(I) Halides and Neutral Heterocyclic Thiones with New Coordination Modes

Reaction of copper(I) chloride or bromide with equimolar amounts of the neutral pyrimidine-2-thione ligand (pymtH)
afforded linear chain polymers [Cu(pymtH)X]n (X = Cl, Br) with the pymtH ligand acting as a bridging N, S donor.
In contrast, copper(I) iodide under the same conditions gave the dimeric complex [Cu(pymtH)2I]2 with the pymtH
ligand adopting monodentate coordination mode through the exocyclic sulfur atom in terminal and bridging modes.
Reactions of the heterocyclic thione ligand 2,4,6-trimercaptotriazine (H3TMT) with copper(I) halides afforded novel
three-dimensional polymers, which crystallized in the cubic space group Pa3̄. Each copper(I) ion is coordinated by
three S atoms of three distinct H3TMT ligands, and each H3TMT acts as a tridentate bridging ligand linking three
copper(I) ions through its sulfur atoms, thus forming two independent three-dimensional (3D) networks. The network
belongs to a three-connected (10, 3)-a topology, which is enantiometric and interpenetrating. In all complexes the
ligands are present in the thione form, and all halides are terminally coordinated to copper(I) ions. The
photoluminescent and thermal properties of the complexes have also been investigated.