TY - JOUR
T1 - Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units
AU - Liu, Pibo
AU - Hadjichristidis, Nikos
N1 - KAUST 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).
PY - 2021/10/4
Y1 - 2021/10/4
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/672171
UR - https://pubs.acs.org/doi/10.1021/acsmacrolett.1c00514
U2 - 10.1021/acsmacrolett.1c00514
DO - 10.1021/acsmacrolett.1c00514
M3 - Article
C2 - 35549048
SN - 2161-1653
SP - 1287
EP - 1294
JO - ACS Macro Letters
JF - ACS Macro Letters
ER -