Supramolecular Chemistry Based on [W3S4(H2O)6Cl3]+ − A Versatile Building Block

The cluster [W3S4(H2O)6Cl3]+ (which is present in solutions of [W3S4(H2O)9]4+ in 1−4 M HCl) reacts with the macrocyclic cavitand cucurbituril (C36H36N24O12) to form supramolecular adducts of 2:1 cluster/cucurbituril stoichiometry, where two portals of cucurbituril (which contains a water molecule in its cavity) are closed by two cluster cations. These aggregates are bound together in the solid by complementary hydrogen bonds between coordinated Cl− and the cations H9O4+ to give chains. Thus, a supramolecular architecture is achieved from three different but complementary building blocks. The packing of the chains affords a honeycomb structure (hexagonal symmetry) with channels (about 5.2 Å in diameter). The overall stoichiometry is (H9O4){[W3S4(H2O)6Cl3]2(C36H36N24O12)}Cl3·16.15H2O (1). [W3S4(H2O)6Cl3]+ reacts with SbCl3 in 6 M HCl to give cuboidal [W3(SbCl3)S4(H2O)6Cl3]+, which forms with the macrocyclic cavitand cucurbituril a 2:1 cluster/cucurbituril adduct − a discrete supramolecule consisting of five independent molecular units. In the solid it crystallizes as a salt of very rare anion [SbCl6]3− with the stoichiometry {[W3(SbCl3)S4(H2O)6Cl3]2(C36H36N24O12)}(SbCl6)2/3·12H2O (2). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)