Biradical with a polyfluorinated terphenylene backbone
Biradical with a polyfluorinated terphenylene backbone
复制标题
DOI：
10.1007/s11172-022-3577-0
复制
发表时间：
2022-08-01
影响因子：
1.7
通讯作者：
Tretyakov，E.
中科院分区：
文献类型：
--
作者：
Fedyushin，P. A.;Serykh，A. A.;Tretyakov，E.
以全氟氯苯和锌粉为原料，在KF存在下，C6 F5 ZnCl和（C6 F5）2 Zn与十氯联苯反应，合成了全氟-1，1 ′：4′，1 ″-三联苯。全氟1，1 ′：4′，1 ″-三联苯与叔丁胺在高压釜中反应，生成脱氨基产物4，4 ″-双（叔丁胺）全氟1，1 ′：4′，1 ″-三联苯，后者再与间氯过苯甲酸氧化，定量得到一种新的稳定的氮氧自由基4，4 ″-双（N-叔丁基-N-酰氨基）全氟1，1 ′：4′，1 ″-三联苯。通过X射线衍射确定了二胺和双自由基的分子和晶体结构。根据X-射线衍射数据，顺磁部分和芳环的平面相对于彼此显著旋转，导致顺磁中心之间的弱分子内交换相互作用。
A method was developed for the synthesis of perfluoro-1,1′:4′,1″-terphenyl by the reaction of chloroperfluorobenzene with zinc dust followed by the reaction of the resulting mixture of C6F5ZnCl and (C6F5)2Zn with decafluorobiphenyl in the presence of KF. The reaction of perfluoro-1,1′:4′,1″-terphenyl with tert-butylamine in an autoclave gives the aminodefluorination product, 4,4″-bis(tert-butylamino)perfluoro-1,1′:4′,1″-terphenyl, and the oxidation of the latter withm-chloroperbenzoic acid affords a new stable nitroxide biradical 4,4″-bis(N-tert-butyl-N-oxylamino)perfluoro-1,1′:4′,1″-terphenyl in quantitative yield. The molecular and crystal structures of the diamine and the biradical were established by X-ray diffraction. According to the X-ray diffraction data, the planes of the paramagnetic moieties and the aromatic rings are significantly rotated with respect to each other, resulting in weak intramolecular exchange interactions between the paramagnetic centers.