交替聚（间对苯胺）的高自旋自由基阳离子

High-spin radical cations of alternating poly(m-p-anilines).

作者信息

Kulszewicz-Bajer Irena, Zagórska Magorzata, Wielgus Ireneusz, Pawłowski Mariusz, Gosk Jacek, Twardowski Andrzej

机构信息

Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland.

出版信息

J Phys Chem B. 2007 Jan 11;111(1):34-40. doi: 10.1021/jp0641076.

DOI:10.1021/jp0641076

PMID:17201426

Abstract

Three alternating poly(m-p-anilines) have been synthesized via palladium-catalyzed amination reactions. Polymers were oxidized to radical cations by the use of chemical and electrochemical methods. The presence of radical cations was manifested by the appearance of two new bands in UV-vis spectra and a strong EPR signal. Moreover, EPR spectra at low temperatures confirmed the formation of a high-spin state. The magnetization measurements of polymers oxidized to radical cations revealed the paramagnetic-type behavior with weak antiferromagnetic interactions. Radical cations underwent the degradation processes in the presence of air, which led to the decrease of spin concentration.

摘要

通过钯催化胺化反应合成了三种交替的聚（间对苯胺）。通过化学和电化学方法将聚合物氧化为自由基阳离子。紫外可见光谱中出现的两条新谱带和强电子顺磁共振（EPR）信号表明了自由基阳离子的存在。此外，低温下的EPR光谱证实形成了高自旋态。对氧化为自由基阳离子的聚合物进行的磁化测量揭示了具有弱反铁磁相互作用的顺磁型行为。自由基阳离子在空气中会发生降解过程，这导致自旋浓度降低。