A high-spin and durable polyradical: poly(4-diphenylaminium-1,2-phenylenevinylene).
A high-spin and durable polyradical: poly(4-diphenylaminium-1,2-phenylenevinylene).
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一种高自旋且耐用的多自由基：聚(4-二苯基胺-1,2-亚苯基亚乙烯基)。
DOI：
10.1021/jo0302758
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发表时间：
2004
期刊：
影响因子：
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通讯作者：
H. Nishide
中科院分区：
文献类型：
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作者：
Hidenori Murata;Masahiro Takahashi;Kazuaki Namba;Naoki Takahashi;H. Nishide
合成了一种纯有机、高自旋和耐用的聚自由基分子：它是基于π共轭聚（1，2-亚苯基亚乙烯基）主链的非Kekulé-和非不相交设计，该主链被多个鲁棒的芳基铵自由基4-取代。合成了4-N，N-双（4-甲氧基-和-叔丁基苯基）氨基-2-溴苯乙烯5，并在钯膦催化剂作用下聚合得到了头-尾连接的聚合自由基前体（1）。用冠醚增溶的亚硝鎓离子氧化1得到铵多自由基（1（+）（）），其在室温下在空气中持久（半衰期> 1个月）。通过磁化率、磁化强度、ESR和NMR的测量，证明了1a（+）的高自旋基态为平均S = 4.5/2。
A purely organic, high-spin, and durable polyradical molecule was synthesized: It is based on the non-Kekulé- and non-disjoint design of a pi-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)amino-2-bromostyrene 5 were synthesized and polymerized with a palladium-phosphine catalyst to afford the head-to-tail-linked polyradical precursors (1). Oxidation of 1 with the nitrosonium ion solubilized with a crown ether gave the aminium polyradicals (1(+)()) which were durable (half-life > 1 month) at room temperature in air. A high-spin ground state with an average S = (4.5)/2 for 1a(+) was proved even at room temperature by magnetic susceptibility, magnetization, ESR, and NMR measurements.