Heat Capacity Study of the Abrupt Valence-detrapping Phase Transition of Mixed-valence [Mn3O(O2CCH3)6(py)3]⋅ Py
Heat Capacity Study of the Abrupt Valence-detrapping Phase Transition of Mixed-valence [Mn3O(O2CCH3)6(py)3]⋅ Py
复制标题
混合价态突然脱俘相变的热容研究 [Mn3O(O2CCH3)6(py)3]⋅ Py
DOI：
10.1021/ic00325a014
复制
发表时间：
1989
影响因子：
4.6
通讯作者：
D. Hendrickson
中科院分区：
文献类型：
--
作者：
M. Nakano;M. Sorai;J. Vincent;G. Christou;H. Jang;D. Hendrickson
用绝热量热计测定了混合价配合物[Mn 3 O（O2 CCH 3）6（py）3 ]·py（py为吡啶）在13 ~ 300 K之间的热容。在184.65K处发现了一个具有尖锐热容峰的相变。相变的焓和熵分别为ΔH=6460 J mol −1和ΔS=35.77 J K −1 mol −1。通过与单晶X射线衍射、磁化率和固体2 HNMR研究结果的比较，我们认为该相变与混合价Mn 3 O配合物中的快速分子内电子转移和吡啶溶剂化物分子的取向无序有关
The heat capacity of the mixed-valence complex [Mn 3 O(O 2 CCH 3 ) 6 (py) 3 ].py, where py is pyridine, has been measured with an adiabatic calorimeter between 13 and 300 K. A phase transition with a sharp heat capacity peak has been found at 184.65 K. The enthalpy and entropy of the phase transition are ΔH=6460 J mol −1 and ΔS=35.77 J K −1 mol −1 . From a comparison of the present calorimetric results with the results of single-crystal X-ray diffraction, magnetic susceptibility, and solid-state 2 H NMR studies, it is concluded that the phase transition is associated with the onset of rapid intramolecular electron transfert in the mixed-valence Mn 3 O complexes and the orientational disordering of the pyridine solvate molecules