Tetramethyltetrathiafulvalene [(NbOF4)]∞: One-Dimensional Charge Transfer Salt with an Infinite Anion Chain
Tetramethyltetrathiafulvalene [(NbOF4)]∞: One-Dimensional Charge Transfer Salt with an Infinite Anion Chain
复制标题
四甲基四硫富瓦烯 [(NbOF4)]∞：具有无限阴离子链的一维电荷转移盐
DOI：
10.1021/acs.inorgchem.1c00208
复制
发表时间：
2021
影响因子：
4.6
通讯作者：
Sawa Hiroshi
中科院分区：
文献类型：
--
作者：
Nakamura Toshikazu;Zhang Lidong;Kitou Shunsuke;Sawa Hiroshi
合成了一维分子电荷转移盐(TMTTF)(NbOF4)[TMTTF=四甲基四硫富瓦烯]。为了了解(TMTTf)(NbOF4)盐的晶体结构和电子态，我们进行了同步X射线衍射、电子自旋共振和静态磁化强度测量。在(TMTTF)(NbOF4)的晶胞内只有一个独立的TMTTF分子。TMTTF1+阳离子自由基堆积成一维柱。TMTTf分子在晶体中的有效电荷为+1。TMTTf给体的电荷被无限大的阴离子链[(NbOF4)−]∞]补偿。(TMTTf)(NbOF4)的室温磁化率为4×10~(-4)emu/mol，60K以上磁化率随温度变化较小，60K以下磁化率随温度的变化有一定的偏差，在5K以下磁化率随温度的变化曲线偏离直线，呈现饱和趋势。在2K下，用THs=2自旋系统可以很好地再现实验结果。详细分析了(TMTTf)(NbOF4)的晶体结构和反常低温磁态磁性。
An unusual valence one-dimensional (1D) molecular charge transfer salt (TMTTF)(NbOF4) [TMTTF = tetramethyltetrathiafulvalene] with infinite anion chains was prepared. To understand the crystal structure and electronic states of the (TMTTF)(NbOF4) salt, we performed synchrotron X-ray diffraction, electron spin resonance, and static magnetization measurements. There is only one independent TMTTF molecule in the unit cell of (TMTTF)(NbOF4). The TMTTF1+cation radicals stack to form 1D columns. The effective charge of the TMTTF molecule in the crystal was estimated to be +1. The electric charge of TMTTF donors is compensated by the infinite anion chains [(NbOF4)−]∞. The magnetic susceptibility of (TMTTF)(NbOF4) is 4 × 10–4emu/mol at room temperature and shows weak temperature dependence above 60 K. However, some deviation appears below 60 K. The temperature dependence of the spin susceptibility shows a noticeable enhancement below 60 K. Below 5 K, the magnetization curve as a function of the magnetic field deviates from the straight line and shows a saturation tendency. The experimental results can be reproduced well with theS= 2 spin system at 2 K. The detailed analysis of the crystal structure and anomalous low-temperature magnetic state magnetic properties of (TMTTF)(NbOF4) are discussed.