Three New Heterothiometallic Cluster Polymers with Fascinating Topologies

Three new heterothiometallic cluster polymers with fascinating topologies have been synthesized by the self-assembly of preformed heterothiometallic cluster monomers and appropriate ligands. Reaction of the monomeric cubic-shaped cluster [Et4N]3[MoOS3Cu3I4] with the D2h symmetry rigid bidentate 4,4′-bipy (4,4′-bipyridine) gave a two-dimensional (2D) layer compound [Mo2O2S6Cu6I2(4,4′-bipy)3(H2O)]n (1); the assembly of pentanuclear cluster monomer [Et4N]4[WS4Cu4I6] with Cs-symmetrical bpe (1,2-bis(4-pyridyl)ethane) afforded a 2D layer compound [WS4Cu4I2(bpe)3(H2O)]n (2), and the assembly of heptanuclear cluster monomer [Et4N]4[WS4Cu6I8] with D3h symmetry trigonal planar ligand timtz (2, 4, 6-tri(1H-imidazol-1-yl)-1, 3, 5-triazine) afforded a three-dimensional (3D) compound [WS4Cu6I4(timtz)8/3(H2O)12]n (3). X-ray crystallographic analysis reveals that 1 crystallizes in trigonal space group R3̅c with 2D 36-hxl net which is the first heterothiometallic superamolecular structure based on a twin cubic-shaped cluster monomer and also the first example of 4,4′-bipy-connected compound of this net. 2 crystallizes in tetragonal space group P42 with distorted 2D 36-hxl net which is the first flexible-ligand-based compound of this topology; while 3 has a 3D net with the high symmetry of cubic space group I4̅3d, and has a novel α-C3N4 topology, which is the maximum symmetry for this net topology. The gas sorption isotherm was measured for 3 to exhibit type-III sorption behavior.