Synthesis of and ferromagnetic coupling in poly(phenylenevinylene)s bearing built-in t-butyl nitroxides
Synthesis of and ferromagnetic coupling in poly(phenylenevinylene)s bearing built-in t-butyl nitroxides
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内置叔丁基硝基氧的聚亚苯基亚乙烯基的合成和铁磁耦合
DOI：
10.1246/bcsj.69.499
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发表时间：
1996
影响因子：
4
通讯作者：
E. Tsuchida
中科院分区：
文献类型：
--
作者：
H. Nishide;T. Kaneko;Shuichi Toriu;Yoshihiro Kuzumaki;E. Tsuchida
以4-或2-溴-2-或4-[N-叔丁基-N-（三乙基硅氧基或叔丁基二甲基硅氧基）氨基]苯乙烯为原料，分别在钯催化剂作用下聚合，合成了聚[[2-或4-[N-叔丁基-N-（三乙基硅氧基或叔丁基二甲基硅氧基）氨基]-1，4-或1，2-亚苯基]亚乙烯基]。它们被脱保护和化学氧化，产生带有2-或4-取代的内置氮氧自由基的聚（1，4-或1，2-亚苯基亚乙烯基）。聚合自由基是化学稳定的，并且它们的自旋浓度增加到0.8自旋/单位。一个SQUID测量，其中包括相应的双自由基和三自由基表明，部分，但强大的，分子内的铁磁耦合建立通过共轭骨架，尽管在侧自由基部分的自旋缺陷，为聚（1，2- phenylenevinylene）轴承4-取代内置的氮氧自由基。
Poly[[2- or 4-[N-t-butyl-N-(triethylsiloxy- or t-butyldimethylsiloxy)amino]-1,4- or 1,2-phenylene]vinylene] was synthesized by polymerizing 4- or 2-bromo-2- or 4-[N-t-butyl-N-(triethylsiloxy- or t-butyldimethylsiloxy)amino]styrene with a palladium catalyst, respectively. They were deprotected and chemically oxidized to yield poly(1,4- or 1,2-phenylenevinylene)s bearing a 2- or 4-substituted built-in nitroxide radical. The polyradicals were chemically stable, and their spin concentration was increased to 0.8 spin/unit. A SQUID measurement which included the corresponding diradicals and triradicals indicated that a partial, but strong, intramolecular ferromagnetic coupling was established through the conjugated backbone, despite a spin defect in the side radical moiety, for the poly(1,2- phenylenevinylene) bearing 4-substituted built-in nitroxide radical.