Supramolecular Chemistry Based on [W 3 S 4 (H 2 O) 6 Cl 3 ] + − A Versatile Building Block

The cluster [W 3 S 4 (H 2 O) 6 Cl 3 ] + (which is present in solutions of [W 3 S 4 (H 2 O) 9 ] 4+ in 1−4 M HCl) reacts with the macrocyclic cavitand cucurbituril (C 36 H 36 N 24 O 12 ) 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 H 9 O 4 + 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 (H 9 O 4 ){[W 3 S 4 (H 2 O) 6 Cl 3 ] 2 (C 36 H 36 N 24 O 12 )}Cl 3 ·16.15H 2 O ( 1 ) . [W 3 S 4 (H 2 O) 6 Cl 3 ] + reacts with SbCl 3 in 6 M HCl to give cuboidal [W 3 (SbCl 3 )S 4 (H 2 O) 6 Cl 3 ] + , 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 [SbCl 6 ] 3− with the stoichiometry {[W 3 (SbCl 3 )S 4 (H 2 O) 6 Cl 3 ] 2 (C 36 H 36 N 24 O 12 )}(SbCl 6 ) 2/3 ·12H 2 O ( 2 ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)