Temperature dependence of the crystal structure and g-values of [(HC(Ph2PO)3)2Cu](ClO4)2.2H2O: influence of dynamic Jahn-Teller coupling and lattice strain interactions.
Temperature dependence of the crystal structure and g-values of [(HC(Ph2PO)3)2Cu](ClO4)2.2H2O: influence of dynamic Jahn-Teller coupling and lattice strain interactions.
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[(HC(Ph2PO)3)2Cu](ClO4)2.2H2O 的晶体结构和 g 值的温度依赖性：动态 Jahn-Teller 耦合和晶格应变相互作用的影响。
DOI：
10.1021/ic048604h
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发表时间：
2005
影响因子：
4.6
通讯作者：
M. A. Hitchman
中科院分区：
文献类型：
--
作者：
C. Simmons;H. Stratemeier;G. Hanson;M. A. Hitchman
本文报道了[（HC（Ph（2）PO）（3））（2）Cu]（ClO（4））（2）·2 H（2）O的X射线晶体结构和粉末EPR谱随温度的变化，室温结构证实了以前报道的结果。低于约100 K时，数据表明[（HC（Ph（2）PO）（3））（2）Cu]（2+）配合物的几何结构具有近似拉长的四重对称性，但在升温时，两个较高的Cu-O键长和g值逐渐收敛，到340 K时，键长对应于压缩的四重几何结构。假设Cu-O（6）多面体在Jahn-Teller振动耦合和晶格应变作用下的能级平衡，可以令人满意地解释这些数据。然而，只有当温度接近340 K时，晶格应变的正交分量减小到可以忽略的值时，才能得到与实验一致的结果。
The temperature dependence of the X-ray crystal structure and powder EPR spectrum of [(HC(Ph(2)PO)(3))(2)Cu](ClO(4))(2).2H(2)O is reported, and the structure at room temperature confirms that reported previously. Below approximately 100 K, the data imply a geometry with near elongated tetragonal symmetry for the [(HC(Ph(2)PO)(3))(2)Cu](2+) complex, but on warming the two higher Cu-O bond lengths and g-values progressively converge, and by 340 K the bond lengths correspond to a compressed tetragonal geometry. The data may be interpreted satisfactorily assuming an equilibrium among the energy levels of a Cu-O(6) polyhedron subjected to Jahn-Teller vibronic coupling and a lattice strain. However, agreement with the experiment is obtained only if the orthorhombic component of the lattice strain decreases to a negligible value as the temperature approaches 340 K.