Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior.
Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior.
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DOI：
10.1039/b416986g
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发表时间：
2005-02
影响因子：
4
通讯作者：
K. Nakano;N. Suemura;Ko Yoneda;S. Kawata;S. Kaizaki
中科院分区：
文献类型：
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作者：
K. Nakano;N. Suemura;Ko Yoneda;S. Kawata;S. Kaizaki
制备了两种不同类型3-或4-取代吡啶的吡唑啉桥接双核NCS和NCBH3二铁（II）配合物[{Fe(NCS或NCBH3)(X-py)}2(mu-bpypz)2]，并测量了它们的变温磁化率。NCS和nch3配合物的自旋交叉温度Tc与相应的取代吡啶之间存在线性相关，Tc与哈密特常数之间也存在线性相关，支持了配位吡啶的电子取代效应而非空间效应。讨论了配体场和电子间排斥参数以及热力学数据和协同因子与它们的自旋交叉行为的关系。
Two series of pyrazolato bridged dinuclear NCS and NCBH3 diiron(II) complexes with various types of 3- or 4-substituted pyridines, [{Fe(NCS or NCBH3)(X-py)}2(mu-bpypz)2], were prepared and their variable-temperature magnetic susceptibilities were measured. There were found linear correlations of the spin-crossover temperatures Tc not only between the NCS and NCBH3 complexes with the corresponding substituted pyridines, but also between the Tc and the Hammett constants, supporting the electronic substituent effect of the coordinated pyridine rather than a steric effect. The ligand field and the interelectronic repulsion parameters together with the thermodynamic data and/or cooperativity factor were discussed in relation with their spin-crossover behavior.