Formation of Extended 1D and 2D Coordination Polymers in Tetrathioether Complexes of Mercury(II) and Copper(I): Crystal Structures of [{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n]

A one-dimensional (1D) coordination polymer of stoichiometry [{{Ge(CH2SPh)4}HgBr2}n] (2b) has been prepared by treatment of HgBr2 with the functionalized germane Ge(CH2SPh)4 (1b), which is acting as a tetradentate thioether ligands. The extended structure results from weak intermolecular Hg–S interactions linking the monomeric {Ge(CH2SPh)4}HgBr2 units, as established using single-crystal X-ray diffraction. The effective coordination around the mercury atoms is best described as distorted octahedral. Upon reaction of CuI with 1b in a 2:1 metal-to-ligand ratio, the novel metal-organic polymer [{{Ge(CH2SPh)4}(Cu2I2)}n] (3), which incorporates rhombic dinuclear Cu(μ-I)2Cu units within its 2D sheet-like network, was obtained. The luminescence properties of 1b and 3 have been investigated both in solution and in the solid state. Upon treatment of 1b with [{Re(μ-Br)(CO)3(THF)}2] the mononuclear compound fac-[ReBr(CO)3{Ge(CH2SPh)4}] (4) is formed. In this chelate complex, two CH2SPh arms are ligated on ReI, the remaining two CH2SPh arms are dangling.

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