Department of Biology and Chemistry, Institute of Molecular Functional Materials, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
Dalton Trans. 2013 Mar 21;42(11):3876-87. doi: 10.1039/c2dt32331a. Epub 2013 Jan 16.
The synthesis, crystal structures and magnetic properties of six cyano-bridged heterobimetallic compounds prepared from a paramagnetic Ru(III) building block, trans-(PPh(4))[Ru(III)(Q)(2)(CN)(2)] (1) (Q = the anion of 8-hydroxyquinoline), are described. 1 reacts with hydrated MnCl(2) in MeOH or DMF to produce a trinuclear compound {Ru(III)(Q)(2)(CN)(2)[Mn(II)(MeOH)(4)]}·8MeOH (2), or a 1-D zigzag chain {Mn(II)(DMF)(2)(Cl)(2)[Ru(III)(Q)(2)]}(n)(3). The Mn(II) has a distorted octahedral environment in 2 and a trigonal-bipyramidal environment in 3. 1 reacts with [Mn(III)(L(1))(Cl)(H(2)O)] in MeOH to produce the 1-D {Ru(III)(Q)(2)(2)[Mn(III)(L(1))]}(n) (4) that consists of alternating Mn(III) and Ru(III) units. 1 also reacts with [Cu(II)(cyclam)Br(2)] and [Ni(II)(cyclam)Cl(2)] in MeOH to produce the trinuclear complexes Ru(III)(Q)(2)(CN(2))[M(II)(cyclam)] (M = Cu(II) (5) and Ni(II) (6)). On the other hand, the reaction of 1 with [Ni(II)(cyclen)Cl(2)] produces a 1-D zigzag chain {([Ru(III)(Q)(2)(CN(2))][Ni(II)(cyclen)])[Ru(III)(Q)(2)(CN(2))]}(n) (7). Compounds 2-4 exhibit antiferromagnetic coupling between Ru(III) and Mn(III/II) centres. Antiferromagnetic coupling also occurs between Ru(III) and Cu(II) centres in 5. On the other hand, compounds 6 and 7 exhibit ferromagnetic coupling between Ru(III) and Ni(II) through cyanide bridges.
六种氰桥异双核配合物的合成、晶体结构和磁性研究。这些配合物是由顺式-(PPh4)[Ru(III)(Q)(2)(CN)2] (1) (Q 为 8-羟基喹啉的阴离子)与顺磁性 Ru(III)构筑块制备而成。1 与水合 MnCl2在 MeOH 或 DMF 中反应，生成三核化合物{Ru(III)(Q)(2)(CN)2[Mn(II)(MeOH)4] }·8MeOH (2)，或一维锯齿链{Mn(II)(DMF)2(Cl)(2)[Ru(III)(Q)(2)]}(n)(3)。Mn(II)在 2 中具有扭曲的八面体环境，在 3 中具有三角双锥环境。1 与[Mn(III)(L1)(Cl)(H2O)]在 MeOH 中反应，生成一维{Ru(III)(Q)(2)(2)Mn(III)(L1)}(4)，其中包含交替的 Mn(III)和 Ru(III)单元。1 还与[Cu(II)(cyclam)Br2]和[Ni(II)(cyclam)Cl2]在 MeOH 中反应，生成三核配合物Ru(III)(Q)(2)(CN2)[M(II)(cyclam)] (M = Cu(II) (5)和 Ni(II) (6))。另一方面，1 与[Ni(II)(cyclen)Cl2]反应生成一维锯齿链{([Ru(III)(Q)(2)(CN2)][Ni(II)(cyclen)])[Ru(III)(Q)(2)(CN2)]}(n) (7)。化合物 2-4 中 Ru(III)和 Mn(III/II)中心之间表现出反铁磁耦合。化合物 5 中 Ru(III)和 Cu(II)中心之间也存在反铁磁耦合。另一方面，化合物 6 和 7 通过氰桥表现出 Ru(III)和 Ni(II)之间的铁磁耦合。
