Syntheses, Structures And Properties Of Supramolecular Compounds Constructed From The Preformed Mo(W)/S/Cu Clusters

This dissertation was focused on the construction of supramolecular arrays by using of Mo(W)/S/Cu clusters with fixed geometries.The main research results are described as following:1. Treatment of [PPh₄][Cp^*WS₃] with CuCN affords a trinuclear butterfly-shaped core cluster [PPh₄][Cp^*WS₃(CuCN)₂] (1) and a tetranuclear incompleted-cubane shaped cluster [PPh₄MCp*WS₃Cu₃(CN)₃]₂ (4). Further reaction of 1 with PPh₃ (or Py) obtained two different novel double-butterfly-shaped clusters [Cp*WS₃Cu₂(μ-CN)₂(PPh₃)]₂ (2) and [PPh₄][{(η⁵-C₅Me₅)WS₃Cu2(CN)(Py)}₂(μ-CN)](3). On the other hand, five supramolecular arrays were synthesized from the preformed cluster (4) and characterized by spectroscopy and X-ray diffraction. They are: the supramolecular cube structure, [(Cp^*WS₃Cu₃)₈Cl₈(μ-CN)₁₂Li₄] (5), a diamond-like three dimensional network [Cp^*WS₃Cu₃(μ-CN)₂(py)]_∞(6), an infinite anionic chain{[PPh₄][Cp^*WS₃Cu₃(μ₃-Cl)(μ-CN)(CN)]·(py)}_∞ (7), a dimeric compound [PPh₄]₂{[Cp^*WS₃Cu₃(CN)₂]₂(μ-CN)₂}·0.5(4,4'-bpy) (8) and an 1D ladder {Li[(Cp^*WS₃Cu₃Br)₂(CN)₅]} (9). Reaction of [PPh₄]₂[Cp^*WS₃(CuBr)₃]₂ with 4,4'-bipy afforded a neutral 2D array [Cp^*WS₃Cu₃Br(μ-Br)(4,4'-bpy)]_∞ (10). In addition, the synthesis and characterization of the heteronuclear cluster [Cp^*WS₃Au(dppmS)] (11)were discussed in this section.2. The synthesis and absorptive property of an unusual 3D porous coordination polymer 12a assembled from [Et₄N]₄[WS₄Cu₄I₆] and 4,4'-bpy, the structures of 12a·8CH₃CN and its iodine absorbate 12·2I₂ were reported. Three 2D arrays of{[WS₄Cu₄I₂(dps)₂]·2MeOH }_∞ (13·2MeOH), {[WS₄Cu₄(bpds)₂(dca)₂]·MeOH-H₂O}_∞ (14MeOH·H₂O) and {Li[W₂S₈Cu₇Cl₄(1,4-Pz)₂]·2MeOHH₂O}_∞ (15-2MeOHH₂O) were also characterized by spectroscopy and X-ray diffraction.3. Three supramolecular arrays containing [MOOS3C113] cluster core were obtained by use of the preformed cluster [n-Bu4N]2[MoOS3Cu3(SCN)3J and characterized by spectroscopy and X-ray diffraction: the 3D framework of [{[MoOS3Cu3(SCN)]2(4,4'-bipy)5}-6C6H5NH2]oo(16-6C6H5NH2), the infinite ID chain [MoOS3Cu3Cl(bpds)2] (17) and the 2D layer [MoOS3Cu3(dca)(4,4-bpy),.5]-DMFMeOH (18-DMF-MeOH).4. The synthesis of lead(II) 4-trimethylammoniophenylthiolate from lead acetate and 4-trimethylammoniophenylthiol hexafluorophosphate (19) at the room temperature by solid-state reaction, in which case the acetic acid by-product is released as a vapor. The compound even reacted in the solid state with 4,4'-bipyridine to afford the supramolecular compound lead(II) 4-(trimethylammonio)phenylthiolate4,4'-bipyridine (20). All of them were fully characterized by IR, XPS, TQ Luminescence and XRD. Their crystal structures were determined by X-ray diffraction.