Molecular cage and 1-D coordination architectures assembled from silver(I) and dithioether ligands with bulky anthrene spacers: Syntheses, crystal structures, and emission properties

作者：Hu TL; Li JR; Xie YB; Bu XH^*

来源：Crystal Growth & Design, 2006, 6(3): 648-655.

DOI：10.1021/cg050286p

A series of dithioether ligands with bulky anthrene spacers, 9,10-bis[(ethylthio)methyl]anthracene (L-1), 9,10-bis[(n-propylthio)methyl]anthracene (L-2), 9,10-bis[(n-butylthio)methyl]anthracene (L-3), and 9,10-bis[(tert-butylthio)methyl]anthracene (L-4), have been designed and synthesized. The reactions of these ligands with AgX (X = NO3-, ClO4-, PF6-) lead to the formation of six new metal-organic coordination architectures, [Ag-4(L-1)(2)(NO3)(4)](CHCl3)(2) (1), [Ag-4(L-2)(2)(NO3)(4)](CHCl3)(2) (2), [Ag-4(L-3)(2)(NO3)(4)] (3), {[AgL2(CH3CN)](ClO4)}(infinity) (4), {[AgL4(NO3)](2)(CH3CN)}(infinity) (5), and {[AgL4](PF6)}(infinity) (6), which have been characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. Single-crystal X-ray analyses show that complexes 1-3 possess novel tetranuclear molecular cage structures, while 4-6 have chain structures. In 1-3, the S atoms of the ligands take a mu(2)-S bridging coordination mode to link Ag-1 ions; thus four S atoms of two ligands link four Ag-1 ions to form a tetranuclear cage. The differences of ligand terminal groups in L-1, L-2, and L-3 do not greatly influence the structures of their complexes. However, the changes of the terminal groups cause subtle differences in the coordination geometry of the Ag-1 centers, the number of solvent molecules encapsulated in the space among adjacent tetranuclear moieties, and the packing mode of the tetranuclear units. Complex 5, whose ligand bears larger tert-butyl terminal groups, is a one-dimensional (1-D) structure instead of a tetranuclear cage. In addition, the structural differences of 2 and 4 (5 and 6) may contribute to the relatively stronger coordination ability of NO3- than that of ClO4- (or PF6-). These results indicate that the terminal groups of the ligands and the counteranions may play important roles in governing the structural topologies of such metal-organic coordination architectures. Furthermore, complexes 1-6 also display strong blue emissions in the solid state at room temperature.

• 出版日期2006-3
• 单位南开大学