Rodríguez-Diéguez A, Palacios M A, Sironi A, Colacio E
Dipartimento di Chimica Strutturale e Stereochimica Inorganica, CNR-ISTM, Università di Milano, via Venezian 21, 20133, Milano, Italy.
Dalton Trans. 2008 Jun 7(21):2887-93. doi: 10.1039/b801306c. Epub 2008 Apr 21.
The bimetallic complex [CoNi(pmzt)4] (pmtz- = 5-(pyrimidyl)tetrazolate ligand) has been prepared by hydrothermal treatment of an equimolecular mixture of the mononuclear complexes[Co(pmtz)2(H2O)2] and [Ni(pmtz)2(H2O)2]. The structure of [CoNi(pmzt)4] consists of (4,4) square-grid-like sheets, in which Co(II) and Ni(II) metal ions are connected by pmtz(-) bridging ligands. This compound is a spin-canted antiferromagnet (weak ferromagnet) with Tc = 18 K. Although Co(II) and Ni(II) ions have different spin values, the spin-canted structure can be formed because of the accidental compensation of their magnetic moments. Both magnetic anisotropy and antisymmetric exchange interaction promote the spin canting of the compensated magnetic moments in the 3D antiferromagnetic phase. On passing from the homometallic complex, [Co2(pmzt)4], which is also a spin-canted antiferromagnet with Tc = 15 K, to the bimetallic complex, [CoNi(pmzt)4], Tc increases and the hysteresis parameters, remnant magnetization (Mr) and critical field (Hc), decrease. The increase in Tc may be a consequence of the increase of the JCoNi, whereas the decrease in Mr and Hc is probably due to the presence in [CoNi(pmzt)4] of a lower content of the highly anisotropic Co(II) ion.
通过对单核配合物[Co(pmtz)₂(H₂O)₂]和[Ni(pmtz)₂(H₂O)₂]的等分子混合物进行水热处理,制备了双金属配合物[CoNi(pmzt)₄](pmtz⁻ = 5-(嘧啶基)四唑配体)。[CoNi(pmzt)₄]的结构由(4,4)方形网格状薄片组成,其中Co(II)和Ni(II)金属离子通过pmtz⁻桥连配体相连。该化合物是一种自旋倾斜反铁磁体(弱铁磁体),居里温度Tc = 18 K。尽管Co(II)和Ni(II)离子具有不同的自旋值,但由于它们磁矩的偶然补偿,可以形成自旋倾斜结构。磁各向异性和反对称交换相互作用都促进了三维反铁磁相中补偿磁矩的自旋倾斜。从同金属配合物[Co₂(pmzt)₄](它也是一种自旋倾斜反铁磁体,Tc = 15 K)转变为双金属配合物[CoNi(pmzt)₄]时,Tc升高,而磁滞参数、剩余磁化强度(Mr)和临界场(Hc)降低。Tc的升高可能是JCoNi增加的结果,而Mr和Hc的降低可能是由于[CoNi(pmzt)₄]中高度各向异性的Co(II)离子含量较低。