Three New Heterothiometallic Cluster Polymers with Fascinating Topologies

Abstract

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 [Et(4)N](3)[MoOS(3)Cu(3)I(4)] with the D(2h) symmetry rigid bidentate 4,4'-bipy (4,4'-bipyridine) gave a two-dimensional (2D) layer compound [Mo(2)O(2)S(6)Cu(6)I(2)(4,4'-bipy)(3)(H(2)O)](n) (1); the assembly of pentanuclear cluster monomer [Et(4)N](4)[WS(4)Cu(4)I(6)] with C(s)-symmetrical bpe (1,2-bis(4-pyridyl)ethane) afforded a 2D layer compound [WS(4)Cu(4)I(2)(bpe)(3)(H(2)O)](n) (2), and the assembly of heptanuclear cluster monomer [Et(4)N](4)[WS(4)Cu(6)I(8)] with D(3h) symmetry trigonal planar ligand timtz (2, 4, 6-tri(1H-imidazol-1-yl)-1, 3, 5-triazine) afforded a three-dimensional (3D) compound [WS(4)Cu(6)I(4)(timtz)(8/3)(H(2)O)(12)](n) (3). X-ray crystallographic analysis reveals that 1 crystallizes in trigonal space group R3c with 2D 3(6)-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 P4(2) with distorted 2D 3(6)-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 I43d, and has a novel alpha-C(3)N(4) topology, which is the maximum symmetry for this net topology. The gas sorption isotherm was measured for 3 to exhibit type-III sorption behavior.