Synthesis,crystal structures, and magnetic properties of two three-dimensional octacyanotungstate(IV)-based bimetallic frameworks with 4,4′-bipyridine dioxide (4,4′-dpdo)  

作　　者：YUAN Mei GAO Song ZHAO Fei ZHANG Wen WANG ZheMing 

机构地区：[1]Beijing National Laboratory for Molecular Sciences,and State Key Laboratory of Rare Earth Materials Chemistry and Applications,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China

出　　处：《Science China Chemistry》2009年第3期266-275,共10页中国科学（化学英文版）

基　　金：Supported by the National Natural Science Foundation of China (Nos. 20221101, 20490210, and 20701039);the National Basic Research Program of China (No. 2006CB601102)

摘　　要：The reaction of [HN(n-C4H9)3]3[WV (CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV (CN)8]{·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]{·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) ?, b=11.321(2) ?, c=12.295(3) ? and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) ?, b=13.784(3) ?, c=13.225(3) ?, β=93.44(3)° and Z=4. In complex 1, each [WIV (CN)8]4? unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN? ions forming wavelike alternating-W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV (CN)8]4? ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN? ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnII ions, while complex 2 exhibits a weak ferromagnetic interaction between CuII ions.The reaction of [HN(n-C4H9)3]3[WV(CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV(CN)8]}·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]}·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants a=10.397(2) -, b= 11.321(2) -, c=12.295(3) - and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) -, b=13.784(3) -, c=13.225(3) -, β=93.44(3)o and Z=4. In complex 1, each [WIV(CN)8]4- unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN- ions forming wavelike alternating -W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV(CN)8]4- ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN- ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ m ode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnⅡ ions, while complex 2 ex-hibits a weak ferromagnetic interaction between CuⅡ ions.

关 键 词：octacyanometalates 4 4′-bipyridine dioxide COORDINATION polymer CAVITIES MAGNETISM 

分 类 号：O626[理学—有机化学]