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首页> 外文期刊>Journal of chemical crystallography >Synthesis, Spectroscopy, Luminescence and Structures of Trinuclear and Hexanuclear Cu-I Clusters with 2,4,6-Trimercaptotriazine
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Synthesis, Spectroscopy, Luminescence and Structures of Trinuclear and Hexanuclear Cu-I Clusters with 2,4,6-Trimercaptotriazine

机译：Synthesis, Spectroscopy, Luminescence and Structures of Trinuclear and Hexanuclear Cu-I Clusters with 2,4,6-Trimercaptotriazine

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Copper cluster chemistry with a multifunctional 2,4,6-trimercaptotriazine thio-ligand in the presence of triphenylphosphine as a co-ligand is investigated. In a typical case, a reaction of copper(I) chloride with 2,4,6-trimercaptotriazine (tmtH(3)) in a mixture of acetonitrile-methanol at room temperature, followed by the addition of solid Ph3P (1:1:2 molar ratio) yielded a yellow compound of composition, Cu3Cl2(tmtH(2))(PPh3)(6) 1. However, this reaction when performed in dimethyl formamide (DMF) in the presence of Et3N Lewis base (Cu:tmtH(3):PPh3::1:1:2 molar ratio) yielded yellow crystals of hexa-nuclear cluster, Cu-6(tmt)(2)(PPh3)(6).(DMF)(2)2. A single crystal x-ray crystallography revealed that in tri-nuclear cluster 1, all three sulfur donor atoms are bonded to three Cu-I ions, resulting in the two four coordinated Cu(S,Cl,P-2) and one Cu(N,S,P-2) cores. As regards hexa-nuclear cluster 2, each Cu is bonded to one N, one S and one P donor atom, generating six Cu(N,S,P) coordination cores, and each Cu has a distorted trigonal planar geometry. Two parallel triazine rings are held in a close proximity of 3.063 angstrom by six Cu-S bridges. Spectroscopic, luminescence and versatility of bonding modes are described. The tri-nuclear cluster, with a new coordination mode of (tmtH(2))(-), represents a rare example in copper-heterocyclic-2-thione chemistry. Graphic Abstract Copper(I) chloride with tmtH(3) in acetonitrile-methanol mixture has afforded a novel trinuclear luminescent cluster. Reaction of copper(I) chloride with 2,4,6-trimercaptotriazine and PPh3 in CH3CN-CH3OH mixture yielded a trinuclear luminescent cluster of composition, Cu3Cl2(tmtH(2))(PPh3)(6).

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