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Published on: May 12, 2023
Synthesis and crystal structures of multidimensional coordination polymers based on W/Cu/S clusters with flexible
Li Song1, Jianrong Li, Ping Lin
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002, PR China.
Abstract:
Reactions of [WES3]2- (E = S, O) with CuX (X = NCS, CN, I) in the presence of bix (bix = 1,4-bis(imidazole-1-ylmethyl)benzene) in DMF or CH3CN resulted in the formation of two novel 2D --> 3D interpenetrating coordination polymers [S2W2S6Cu4(bix)2]n (1) and {[WS4Cu4(NCS)2(bix)3].CH3CN}n (2), a noninterpenetrating 3D polymer {[WS4Cu2(bix)].DMF}n (3), and two 2D sheet polymers [WS4Cu3(CN)(bix)]n (4) and {[OWS3Cu3(bix)2][I].DMF.2H2O}n (5), depending on the reaction temperature and the reagents used. Compound 1 contains a hexagonal prism of W2Cu4S6 cluster core, which serves as a 4-connecting node to link equivalent nodes via bix ligands, forming a 2D (4,4) net. In 2, a WCu4S4 core, which also acts as a 4-connecting node, connects the neighboring nodes either through single or double bix bridges, affording a different 2D (4,4) sheet. Inclined interpenetration occurs between two stacks of 2D sheets in the total structure of 1, while 2 involves a parallel interpenetration between the adjacent layers, both creating a 3D network. Compounds 1 and 2 represent the first examples of interpenetrating (4,4) frameworks with clusters as nodes and bidentate pyridyl-based ligands as linkers. Unlike 1 and 2, compound 3 has a noninterpenetrating 3D network, which is composed of the inorganic 1D (WS4Cu2)n chains linked by cis and trans bix ligands. Compound 4 features an inorganic 1D (WS4Cu3)n chain structure, which is linked by CN groups and bix ligands to form an infinite 2D network. Compound 5 is a 2D layer polymer with large inner cavities.
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