American Chemical Society
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Solvent-Induced Assembly of Octacyanometalates-Based Coordination Polymers with Unique afm1 Topology and Magnetic Properties

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journal contribution
posted on 2013-12-04, 00:00 authored by Jun Qian, Jingchun Hu, Jinfang Zhang, Hirofumi Yoshikawa, Kunio Awaga, Chi Zhang
Aqueous solution was introduced into the self-assembly of water-insoluble (Bu3NH)3[M­(CN)8] (M = W, Mo) and Mn­(NO3)2·6H2O to afford two, three-dimensional (3D) coordination polymers (CPs), {[μ8-MV(CN)8MnII2(H2O)2(CH3OH)]­[NO3]}n (M = W 1, Mo 2), while polymer {[μ4-WV(CN)8MnII2(DMF)8]­(ClO4)}n (DMF = N,N-dimethylformamide) (3) was crystallized from the reaction of (Bu3NH)3[W­(CN)8] and Mn­(ClO4)2·6H2O in DMF. All three CPs 1, 2, and 3 have been well-characterized by elemental analysis, infrared spectra, single-crystal X-ray diffraction, as well as thermogravimetric analysis. The single-crystal X-ray structural analysis shows that both CPs 1 and 2 crystallize in the monoclinic crystal system with space group of C2/c and possess the infinite 3D framework in an unprecedented afm1 topology geometry, which is an unreported 4-nodal 4,4,8,8-coordinated net with point symbol {411.612.85}­{417.610.8}­{45.6}4. Polymer 3 crystallizes in the space group of P42/m as a 3D supermolecule structure, which is constructed by one-dimensional (1D) cationic {[μ4-WV(CN)8MnII2(DMF)8]+}n chains linked via the hydrogen bonds. Magnetic susceptibility measurements in the temperature range of 2–300 K reveal that CPs 1 and 2 exhibit the similar typical antiferromagnetic properties, while CP 3 shows the ferromagnetic property.