Wang De, Hadjichristidis Nikos
Ocean University of China, School of Medicine and Pharmacy, Qingdao, Shandong Province, 266071, China.
King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering Division, KAUST Catalysis Center, Polymer Synthesis Laboratory, Thuwal, 23955, Kingdom of Saudi Arabia.
Angew Chem Int Ed Engl. 2019 May 6;58(19):6295-6299. doi: 10.1002/anie.201901094. Epub 2019 Apr 1.
The first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers was achieved by one-pot borane-initiated random copolymerization of ω-methylallyl (C3 units, chain is growing by three carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain is growing by one carbon atom at a time) ylides, followed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well-defined, possess a predictable molecular weight and low polydispersity (M =1.83-9.68×10 g mol , Đ=1.09-1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as confirmed by fluorescence and NMR spectroscopy. This phenomenon can be explained by the isomerization of the double bonds of allylic monomeric units along the chain of the terpolymers (isomerization-induced light emission).
通过一锅法硼烷引发的ω-甲基烯丙基（C3单元，链每次增长三个碳原子）和苄基三苯基砷鎓（C1单元，链每次增长一个碳原子）叶立德的无规共聚，随后进行亚甲基氧化硫鎓（C1单元）的聚合反应，首次合成了结构明确的聚[（苯基亚甲基-共-甲基丙烯基）-b-亚甲基，[（C1-共-C3）-b-C1]三元共聚物。也可以使用其他取代的砷鎓叶立德，如异戊烯基三苯基、丙基三苯基和（4-氟苄基）三苯基来代替苄基三苯基砷鎓。所得到的三元共聚物结构明确，具有可预测的分子量和低多分散性（M = 1.83 - 9.68×10⁴ g·mol⁻¹，Đ = 1.09 - 1.22）。通过荧光和核磁共振光谱证实，在这些非共轭三元共聚物中发现了意外的发光现象。这种现象可以通过三元共聚物链上烯丙基单体单元双键的异构化来解释（异构化诱导发光）。
