Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012, USA.
Chemistry. 2010 Jun 25;16(24):7164-73. doi: 10.1002/chem.201000128.
Two families of cationic cyanide-bridged complexes, namely, {Co(triphos)(CN)(2)[M(MeOH)(4)]}(ClO(4))(2) ([Co(2)M] M=Mn, Fe, Co, and Ni; triphos=1,1,1-tris((diphenylphosphino)methyl)ethane) and {Co(triphos)(CN)(2)M(MeOH)(4)}(ClO(4))(4) ([Co(2)M(2)] M=Mn and Ni) have been prepared from reactions of [Co(II)(triphos)(CN)(2)] and M(ClO(4))(2).6H(2)O (M=Mn, Fe, Co, Ni) in methanol. The trinuclear complexes [Co(2)Mn], [Co(2)Fe], and [Co(2)Co], as well as both new tetranuclear complexes [Co(2)Mn(2)] and [Co(2)Ni(2)], exhibit antiferromagnetic coupling between metal centers. In contrast, the [Co(2)Ni] is characterized by ferromagnetic interactions between the Co(II) and Ni(II) centers. The magnetic behavior for these complexes was investigated by DFT calculations and was found to derive from overlap patterns of the different magnetic orbitals as influenced by the angles of the cyanide bridges.
两种阳离子氰桥配合物家族，即 {Co(triphos)(CN)(2)[M(MeOH)(4)]}(ClO(4))(2) ([Co(2)M] M=Mn, Fe, Co, 和 Ni; triphos=1,1,1-tris((diphenylphosphino)methyl)ethane) 和 {Co(triphos)(CN)(2)M(MeOH)(4)}(ClO(4))(4) ([Co(2)M(2)] M=Mn 和 Ni)，是由[Co(II)(triphos)(CN)(2)] 和 M(ClO(4))(2).6H(2)O (M=Mn, Fe, Co, Ni)在甲醇中的反应制备的。三核配合物 [Co(2)Mn]、[Co(2)Fe] 和 [Co(2)Co]，以及两个新的四核配合物 [Co(2)Mn(2)] 和 [Co(2)Ni(2)]，显示出金属中心之间的反铁磁耦合。相比之下，[Co(2)Ni]的特征是 Co(II)和 Ni(II)中心之间的铁磁相互作用。这些配合物的磁行为通过 DFT 计算进行了研究，发现源自不同磁性轨道的重叠模式，这些重叠模式受到氰桥角度的影响。
