Formation of High-Spin States (S = 3/2 and 2) in Linear Oligo- and Polyarylamines

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• 作者：艁ukasz Sk贸rka ; Jean-Marie Mouesca ; Lionel Dubois ; Ewa Szewczyk ; Ireneusz Wielgus ; Vincent Maurel ; Irena Kulszewicz-Bajer
• 刊名：Journal of Physical Chemistry B
• 出版年：2015
• 出版时间：October 22, 2015
• 年：2015
• 卷：119
• 期：42
• 页码：13462-13471
• 全文大小：561K
• ISSN：1520-5207

文摘

This article describes the study of a linear trimer and three polyarylamines PB1鈥? containing a 3,4鈥?biphenyl ferromagnetic coupler. The synthesis of the model compound (trimer) and the polymers has been presented. The formation of radical cations was studied using electrochemical and optical (UV鈥搗is) methods. The chemical oxidation of these compounds leads to the creation of high-spin states, evidenced by pulsed EPR nutation spectroscopy. A quartet spin state is observed for the trimer model compound, and its J exchange coupling constant has been measured experimentally (J/k = 11.8 K) and compared quantitatively to DFT calculations. Most importantly, quartet and quintet spin states have been formed for PB3 and PB2, respectively. These last two doped polymers thus exhibit the highest spin states observed to date for linear polyarylamine compounds.