Syntheses and Properties of (Nitronyl nitroxide)‐substituted Tri‐phenylamine ortho ‐Bridged by Two Oxygen and Sulfur Atoms
Syntheses and Properties of (Nitronyl nitroxide)‐substituted Tri‐phenylamine ortho ‐Bridged by Two Oxygen and Sulfur Atoms
复制标题
两个氧和硫原子邻桥取代的(硝基硝基氧)三苯胺的合成和性能
DOI：
10.1002/asia.202001227
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Okada Keiji
中科院分区：
文献类型：
--
作者：
Yokoyama Naoki;Tanaka Nobuaki;Fujimoto Natsumi;Tanaka Rika;Suzuki Shuichi;Shiomi Daisuke;Sato Kazunobu;Takui Takeji;Kozaki Masatoshi;Okada Keiji
将硝酰基氮氧单元（NN）与基于三苯胺的稠合多环二酮DOTT连接以形成自由基取代的供体NN-DOTT。X射线晶体结构分析表明DOTT单元为平碗状。EPR谱表明电子自旋在NN单元上局域化。DOTT单元的化学氧化产生了自由基取代的自由基阳离子盐NN-DOTT+ NaSbF 6 −和NN-DOTT+ NaFeBr 4 −，它们在环境条件下是稳定的。NN ‐DOTT+<$SbF6 −的磁性特征是NN和DOTT+之间存在强的分子内铁磁相互作用。NN ‐DOTT+ FeBr 4 −的X射线结构分析显示了DOTT的平面结构和NN ‐DOTT+和FeBr 4 −的一维混合堆柱状结构。磁性测量表明，在7 K时，NN ‐DOTT+ FeBr 4 −经历磁相变，成为弱铁磁体。
A nitronyl nitroxide unit (NN) was linked with a triphenylamine‐based condensed polycyclic skeletonDOTTto form a radical substituted donorNN‐DOTT. X‐ray crystal structure analysis demonstrated a flat bowl shape of theDOTTunit. EPR spectra showed the localization of electron spin on theNNunit. Chemical oxidation of theDOTTunit produced radical‐substituted radical cation saltsNN‐DOTT+⋅ SbF6−andNN‐DOTT+⋅ FeBr4−that are stable under ambient conditions. The magnetic behavior ofNN‐DOTT+⋅ SbF6−is characterized by the strong intramolecular ferromagnetic interaction betweenNNandDOTT+. The X‐ray structural analysis ofNN‐DOTT+⋅ FeBr4−shows planar structure ofDOTTand 1D mixed‐stack column ofNN‐DOTT+and FeBr4−. Magnetic measurements established thatNN‐DOTT+⋅ FeBr4−undergoes magnetic phase transition into a weak ferromagnet at 7 K.