在分数还原态下将Fe(II)阳离子配合物与TCNQ结合的导电自旋交叉化合物。
The Conducting Spin-Crossover Compound Combining Fe(II) Cation Complex with TCNQ in a Fractional Reduction State.
作者信息
Shvachko Yuri N, Starichenko Denis V, Korolyov Aleksander V, Yagubskii Eduard B, Kotov Alexander I, Buravov Lev I, Lyssenko Konstantin A, Zverev Vladimir N, Simonov Sergey V, Zorina Leokadiya V, Shakirova Olga G, Lavrenova Lyudmila G
机构信息
M. N. Miheev Institute of Metal Physics, Ural Branch of Russian Academy of Sciences , S. Kovalevskaya Street 18, Yekaterinburg 620137, Russia.
Institute of Problems of Chemical Physics, Russian Academy of Sciences , Semenov Avenue 1, Chernogolovka, 142432 Moscow District, Russia.
出版信息
Inorg Chem. 2016 Sep 6;55(17):9121-30. doi: 10.1021/acs.inorgchem.6b01829. Epub 2016 Aug 19.
The radical anion salt Fe{HC(pz)3}23 demonstrates conductivity and spin-crossover (SCO) transition associated with Fe(II) complex cation subsystem. It was synthesized and structurally characterized at temperatures 100, 300, 400, and 450 K. The compound demonstrates unusual for 7,7,8,8,-tetracyanoquinodimethane (TCNQ)-based salts quasi-two-dimensional conductivity. Pronounced changes of the in-plane direct-current resistivity and intensity of the electron paramagnetic resonance (EPR) signal, originated from TCNQ subsystem, precede the SCO transition at the midpoint T* = 445 K. The boltzmannian growth of the total magnetic response and structural changes in the vicinity of T* uniquely show that half [Fe{HC(pz)3}2] cations exist in high-spin state. Robust broadening of the EPR signal triggered by the SCO transition is interpreted in terms of cross relaxation between the TCNQ and Fe(II) spin subsystems.
自由基阴离子盐Fe{HC(pz)₃}₂₃表现出与Fe(II)络合阳离子子系统相关的导电性和自旋交叉（SCO）转变。它在100、300、400和450 K的温度下被合成并进行了结构表征。该化合物表现出基于7,7,8,8-四氰基对苯二醌二甲烷（TCNQ）的盐所不寻常的准二维导电性。源自TCNQ子系统的面内直流电阻率和电子顺磁共振（EPR）信号强度的显著变化先于中点T* = 445 K处的SCO转变。总磁响应的玻尔兹曼增长以及T*附近的结构变化独特地表明，一半的[Fe{HC(pz)₃}₂]阳离子以高自旋态存在。由SCO转变引发的EPR信号的强烈展宽是根据TCNQ和Fe(II)自旋子系统之间的交叉弛豫来解释的。
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