科研之友
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摘要
Six new silver ethynediide complexes containing trifluoroacetate and ligands derived from isomeric dicyanobenzenes, namely 2Ag(2)C(2)center dot 10AgCF(3)CO(2)center dot 3L(1) (L-1 = 1,2-dicyanobenzene) (1), 2Ag(2)C(2)center dot 10AgCF(3)CO(2)center dot AgNO3 center dot 4L(2) (L-2 = 1,3-dicyanobenzene) (2), Ag2C2 center dot 2AgCF(3)CO(2)center dot 2AgL(3)H center dot H2O ((LH2)-H-3 = benzene-1,3-dicarboxylic acid) (3), Ag2C2 center dot 2AgCF(3)CO(2)center dot(AgLH)-H-3 center dot AgL4 ((LH)-H-4 = 3-cyanobenzenecarboxylic acid) (4), Ag2C2 center dot 4AgCF(3)CO(2)center dot 2AgL(5)center dot 4H(2)O ((LH)-H-5 = 4-cyanobenzenecarboxylic acid) (5) and 2Ag(2)C(2)center dot 6AgCF(3)CO(2)center dot 4AgL(5)center dot Ag2L6 ((LH2)-H-6 = benzene-1,4-dicarboxylic acid) (6), have been synthesized under hydrothermal conditions and characterized using single crystal X-ray analysis. The L-n (n = 1-6) ligands incorporated into the silver ethynediide reaction system were generated in situ from hydrolysis of the o-, m- or p-isomers of dicyanobenzene. In the crystal structures of compounds 1-6, there are various types of silver(I) cages each enclosing a C-2(2-) dianion, which can be regarded as a multinuclear metal-ligand supramolecular synthon and symbolized as C-2@Ag-n (n = 6-8). The silver cages are fused into infinite silver chains, which are connected by dicyanobenzene derivatives to yield two- and three-dimensional coordination networks in 1 and 2-6, respectively. The coordination capacity and structure-directing effect of the L-n ligands, as well as the temperature and pH value of the reaction mixture on the crystal structure of the resulting products, were also investigated.
