Diamond- and Graphite-Like Octacyanometalate-Based Polymers Induced by Metal Ions

Authors

  • Ying Wang Dr.,

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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  • Tian-Wei Wang,

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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  • Hong-Ping Xiao,

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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  • Yi-Zhi Li Dr.,

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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  • You Song,

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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  • Xiao-Zeng You Prof.

    1. State Key Laboratory of Coordination Chemistry, Nanjing, National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University (China), Fax: (+86) 25 83314502
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Abstract

By using cyclohexane-1,2-diamine (chxn), Ni(ClO4)26H2O and Na3[Mo(CN)8]4H2O, a 3D diamond-like polymer {[NiII(chxn)2]2[MoIV(CN)8]8H2O}n (1) was synthesised, whereas the reaction of chxn and Cu(ClO4)26H2O with Na3[MV(CN)8] 4H2O (M=Mo, W) afforded two isomorphous graphite-like complexes {[CuII(chxn)2]3[MoV(CN)8]22H2O}n (2) and {[CuII(chxn)2]3[WV(CN)8]22H2O}n (3). When the same synthetic procedure was employed, but replacing Na3[Mo(CN)8]4H2O by (Bu3NH)3[Mo(CN)8]4H2O (Bu3N=tributylamine), {[CuII(chxn)2MoIV(CN)8][CuII(chxn)2] 2H2O}n (4) was obtained. Single-crystal X-ray diffraction analyses showed that the framework of 4 is similar to 2 and 3, except that a discrete [Cu(chxn)2]2+ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond- or graphite-like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [MoIV(CN)8] bridges mediate very weak antiferromagnetic coupling between the NiII ions in 1, but lead to the paramagnetic behaviour in 4 because [MoIV(CN)8] weakly coordinates to the CuII ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the CuII and WV/MoV ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the WV and CuII ions than between the MoV and CuII ions.

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