Assembly Of Supermolecular Compounds From The Preformed Cluster [MS₄(CuCN)₂]～(2-)(M=Mo, W)

Recently, synthesis of new cluster-containing supermolecular compounds has become one active topic in inorganic chemistry mainly due to the potential applications in industrial catalysis, biological systems and photonic materials.The thesis reports the preparation of [A]2[MS4(CuCN)2] [A = Et4N+, M = Mo (la); A = PPh/, M = Mo (Ib); A = Et4N+, M = W (2a); A = PPh4/, M = W (2b)] by reactions of (NH4)2MS4 (M = Mo, W) with CuCN and ABr (A = PPh4+, EUN+). Compound 2a reacts with Cul in pyridine to form [WS4Cu4(Py)4(CN)2]n (3), while 2a and 2b react with complexes [Cu(CH3CN)4]BF4, [Ag(PPh3)]NO3, affording {[A][WS4Cu3(CN)2]}n [A = PPh4+ (4a), Et4N+ (4b)] and [WS4Cu2(CN)Ag(PPh3)]n (5), respectively. When 2a is treated with [Cu(CH3CN)4]BF4 and 4,4!~bipy, [WS4Cu3(CN)(4,4'-bipy)2]n (6) is produced. In acidic conditions, la or 2a is induced to polymerize into new 2D polymeric clusters [(Et4N)i.5MS4Cu2(CN)1.5]n [M = Mo (7a), W (7b)j. Clusters la-7b were characterized by elemental analysis, IR spectra and the structures of la, 2b, 3, 4a, 7a and 7b were determined by X-ray crystallography. The structures of la and 2b have a linear framework with an approximate D2d symmetry. 3 has a ID ladder-typed structure, while 4a, 7a and 7b exhibit intriguing 2D structures.The successful isolation of 3-7b from the preformed clusters 1-2 not only adds new members into the Mo(W)/Cu(Ag)/S cluster family, but also offers more opportunities for the development of new Mo(W)/Cu(Ag)/S cluster-based NLO materials.