Two novel allylic arsonium ylide monomers with a phenyl (steric and electronic effect) group at different positions were synthesized and used in boron-catalyzed polymerization to produce a series of well-defined polymers, poly(2-phenyl-propenylene-co-2-phenyl-propenylidene) (P2-PhAY) and poly(3-phenyl-propenylene-co-3-phenyl-propenylidene) (P3-PhAY), with unusual structures but a controllable molecular weight and relatively low polydispersity. The backbone of these polymers consists of a mixture of C1 (chain grows by one carbon atom at a time) and C3 (chain grows by three carbon atoms at a time) monomeric units, as determined by 1H, 13C, and 1H–13C HSQC 2D NMR. Based on the experimental results and density functional theoretical (DFT) calculations, we were able to propose a mechanism that takes into account not only the steric hindrance, but also the electron effect of the phenyl group. In addition, a nontraditional intrinsic luminescence was observed from the nonconjugated P2-PhAY and P3-PhAY; such unexpected emission is attributed to the formation of C3-unit clusters, as evidenced by ultraviolet–visible and fluorescence spectroscopy.
Bibliographical noteKAUST Repository Item: Exported on 2021-10-07
Acknowledgements: The research reported in this publication was supported by the King Abdullah University of Science (KAUST) and Technology and the fellowship of the China Postdoctoral Science Foundation (2021M693113).
ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
- Materials Chemistry
- Polymers and Plastics