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Formation of Four Different [MoOS3Cu3]-Based Coordination Polymers from the Same Components via Four Synthetic Routes

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journal contribution
posted on 04.03.2009, 00:00 authored by Jin-Xiang Chen, Xiao-Yan Tang, Yang Chen, Wen-Hua Zhang, Ling-Ling Li, Rong-Xin Yuan, Yong Zhang, Jian-Ping Lang
Assembly of different [MoOS3Cu3]-based coordination polymers from the same components ([(n-Bu)4N]2[MoOS3Cu3(NCS)3] (1) and 4,4′-bypyridine (4,4′-bipy)) via different synthetic approaches has been investigated. Treatment of 1 with 4,4′-bipy (molar ratio = 1:1) in aniline afforded {[{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)3]·6(ani)}n (ani = aniline) (2), while solid state reaction of 1 with equimolar 4,4′-bipy at ambient temperature followed by extraction with aniline yielded {[(n-Bu)4N]2[{MoOS3Cu3(NCS)2}2(4,4′-bipy)3]·2(ani)}n (3). Diffusion reactions of an aniline solution of 1 with an aniline solution of 4,4′-bipy in a straight or zigzag glass tube resulted in the formation of {[MoOS3Cu3(NCS)(4,4′-bipy)2.5]·3(ani)}n (4) and {[(MoOS3Cu3)2(NCS)(μ-NCS)(4,4′-bipy)4.5]·7(ani)}n (5), respectively. Compounds 25 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compounds 2 consists of a 1D zigzag chain in which the dimeric [{MoOS3Cu3(NCS)(ani)2}2(4,4′-bipy)2] units are linked by single 4,4′-bipy bridges, while 3 possesses a one-dimensional spiral chain built of the dimeric [{MoOS3Cu3(NCS)2}2(4,4′-bipy)2] units bridged by 4,4′-bipy ligands. Compound 4 contains a three-dimensional (3D) 3-fold interpenetrated network in which each [MoOS3Cu3] core acts as a tetrahedral four-connecting node to interconnect four other equivalent ones via single and double 4,4′-bipy bridges. Compound 5 has a unique 3D 2-fold interpenetrated network in which the [MoOS3Cu3] cores work as trigonal-pyramidal four- and tetragonal-pyramidal five-connecting nodes to link other equivalent cores through single thiocyanate bridges and single and double 4,4′-bipy bridges. The results may provide interesting insights into effects of synthetic approaches on the construction of cluster-based coordination polymers.