Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Molecular Strands and Related Properties of Silver(Ⅰ) Triflate with 3,3'-Oxybispyridine vs 3,3'-Thiobispyridine

  • Published : 2002.08.20
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Abstract

Studies on subtle spacer ligand effects of AgCF3SO3 with 3,3'-Py2X (X = O vs S) have been carried out. The reaction of AgCF3SO3 with 3,3'-Py2O and 3,3'-Py2S produces [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)] (CF3SO3), respectively. Crystallographic characterization of [Ag(CF3SO3)(3,3'-Py2O)] (monoclinic P1, a =8.405(2) $\AA$, b = 10.714(2) $\AA$, c = 18.031(2) $\AA$, $\alpha=$ 77.36(2), $\beta=107.83(2)^{\circ}$, $\gamma=$ 66.92(2), V = 1438.0(5) $\AA3$ , Z =2,R = 0.0486) reveals that the skeletal structure is an anion-bridged double-strand. The double-strands are packed like a plywood. The framework of [Ag(3,3'-Py2S)](CF3SO3) (orthorhombic Pcab, a = 17.330(2) $\AA$, b = 8.640(1) $\AA$, c = 19.933(6) $\AA$, V = 2985(1) $\AA3$ , Z =8, R = 0.0437) is a sinusoidal single-strand. The formation of each coordination polymer appears to be primarily associated with the donating ability and the confor ma-tional energy barrier of the spacer ligands. Thermal analyses indicate that [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)](CF3SO3) are stable up to 250 $^{\circ}C$ and 210 $^{\circ}C$, respectively. For the anion exchangeability, the nature of the spacer ligand is more significant factor than the distance of silver(Ⅰ)···triflate.

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