Structural Diversities of Silver(I) Coordination Compounds with Flexible Dithioether Ligands Based upon Changing the Ligand Spacers

To investigate the influences of ligand spacers of flexible bis(thioether) bridging ligands on the framework formations of their complexes, six new Ag I coordination compounds with a series of structurally related bis( tert -butylthio)alkane ligands, L n = (CH 3 ) 3 CS-(CH 2 ) n -SC(CH 3 ) 3 where n = 1−6, [(Ag L 1 )ClO 4 ] n ( 1 ), {[Ag( L 2 ) 1.5 ]ClO 4 } n ( 2 ), [(Ag L 3 )ClO 4 ] 2 ( 3 ), {[Ag( L 4 ) 1.5 ]ClO 4 } n ( 4 ), [(Ag L 5 )ClO 4 ] 2 ( 5 ), and {[Ag( L 6 ) 1.5 ]ClO 4 } n ( 6 ), have been synthesized and structurally characterized by elemental analysis, IR, 1 H NMR spectra, and X-ray crystallography. In 1, the Ag I centers are linked by bridging L 1 to form a one-dimensional (1-D) zigzag chain, and complex 2 has an extended two-dimensional (2-D) (6,3) topologic array with hexagonal 30-membered macrometallacycles. Complexes 3 and 5 show similar discrete dinuclear structures. Complexes 4 and 6 consist of single-double bridging chains in which dinuclear macrometallacycles are further linked by single bridging L ligands. The differences among these structures indicate that the spacers of ligands have important effects on the framework formation of their Ag I complexes, and this presents a feasible way for controlling the structures of such complexes by modifying the ligand spacers.