Wang Ying, Wang Tian-Wei, Xiao Hong-Ping, Li Yi-Zhi, Song You, You Xiao-Zeng
State Key Laboratory of Coordination Chemistry, Nanjing, School of Chemistry and Chemical Engineering, Nanjing University, China.
Chemistry. 2009 Aug 3;15(31):7648-55. doi: 10.1002/chem.200900578.
By using cyclohexane-1,2-diamine (chxn), Ni(ClO(4))(2) x 6 H(2)O and Na(3)[Mo(CN)(8)] x 4 H(2)O, a 3D diamond-like polymer {Ni(II)(chxn)(2)[Mo(IV)(CN)(8)] x 8 H(2)O}(n) (1) was synthesised, whereas the reaction of chxn and Cu(ClO(4))(2) x 6 H(2)O with Na(3)[M(V)(CN)(8)] x 4 H(2)O (M = Mo, W) afforded two isomorphous graphite-like complexes {Cu(II)(chxn)(2)Mo(V)(CN)(8) x 2 H(2)O}(n) (2) and {Cu(II)(chxn)(2)W(V)(CN)(8) x 2 H(2)O}(n) (3). When the same synthetic procedure was employed, but replacing Na(3)[Mo(CN)(8)] x 4 H(2)O by (Bu(3)NH)(3)[Mo(CN)(8)] x 4 H(2)O (Bu(3)N = tributylamine), {[Cu(II)(chxn)(2)Mo(IV)(CN)(8)][Cu(II)(chxn)(2)] x 2 H(2)O}(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) 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 [Mo(IV)(CN)(8)] bridges mediate very weak antiferromagnetic coupling between the Ni(II) ions in 1, but lead to the paramagnetic behaviour in 4 because [Mo(IV)(CN)(8)] weakly coordinates to the Cu(II) ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu(II) and W(V)/Mo(V) ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W(V) and Cu(II) ions than between the Mo(V) and Cu(II) ions.
通过使用环己烷 - 1,2 - 二胺（chxn）、Ni(ClO₄)₂·6H₂O和Na₃[Mo(CN)₈]·4H₂O，合成了一种三维类金刚石聚合物{[Ni(II)(chxn)₂]₂[Mo(IV)(CN)₈]·8H₂O}ₙ (1)，而chxn与Cu(ClO₄)₂·6H₂O和Na₃[M(V)(CN)₈]·4H₂O（M = Mo，W）的反应得到了两种同构的类石墨配合物{[Cu(II)(chxn)₂]₃[Mo(V)(CN)₈]₂·2H₂O}ₙ (2)和{[Cu(II)(chxn)₂]₃[W(V)(CN)₈]₂·2H₂O}ₙ (3)。当采用相同的合成方法，但用(Bu₃NH)₃[Mo(CN)₈]·4H₂O（Bu₃N = 三丁胺）代替Na₃[Mo(CN)₈]·4H₂O时，得到了{[Cu(II)(chxn)₂Mo(IV)(CN)₈][Cu(II)(chxn)₂]·2H₂O}ₙ (4)。单晶X射线衍射分析表明，4的骨架与2和3相似，只是4中的离散[Cu(chxn)₂]²⁺部分具有平行相邻层的大通道。实验结果表明，在该体系中，类金刚石或类石墨骨架受到金属离子诱导作用的强烈影响。磁性性质表明，抗磁性的[Mo(IV)(CN)₈]桥介导了1中Ni(II)离子之间非常弱的反铁磁耦合，但由于[Mo(IV)(CN)₈]与Cu(II)离子弱配位，导致4呈现顺磁性行为。对2和3的磁性研究表明，Cu(II)与W(V)/Mo(V)离子之间存在铁磁耦合，并且5d轨道更弥散导致W(V)与Cu(II)离子之间的磁耦合相互作用比Mo(V)与Cu(II)离子之间更强。
