Formation of Extended 1D and 2D Coordination Polymers in Tetrathioether Complexes of Mercury(II) and Copper(I): Crystal Structures of [{{Ge(CH 2 SPh) 4 }HgBr 2 } n ] and [{{Ge(CH 2 SPh) 4 }(Cu 2 l 2 }} n ]

A one‐dimensional (1D) coordination polymer of stoichiometry [{{Ge(CH 2 SPh) 4 }HgBr 2 } n ] ( 2b ) has been prepared by treatment of HgBr 2 with the functionalized germane Ge(CH 2 SPh) 4 ( 1b ), which is acting as a tetradentate thioether ligands. The extended structure results from weak intermolecular Hg–S interactions linking the monomeric {Ge(CH 2 SPh) 4 }HgBr 2 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(CH 2 SPh) 4 }(Cu 2 I 2 )} n ] ( 3 ), which incorporates rhombic dinuclear Cu(μ‐I) 2 Cu 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(CH 2 SPh) 4 }] ( 4 ) is formed. In this chelate complex, two CH 2 SPh arms are ligated on Re I , the remaining two CH 2 SPh arms are dangling.