TY - JOUR
T1 - Novel Terpolymers from Borane Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission
AU - Hadjichristidis, Nikos
AU - Wang, De
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).
PY - 2019/4/1
Y1 - 2019/4/1
N2 - We report the first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers via 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). The synthesized terpolymers possess a predictable molecular weight and monomodal low polydispersity (Mn, NMR=1.83-9.68×103 g /mol, Đ =1.09-1.22). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium ylide, affording well-defined terpolymers too (Mn, NMR=4.3-9.1×103 g/mol, Đ=1.16-1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as demonstrated by fluorescence and NMR spectroscopy. This phenomenon can be attributed to the formation of conjugated small blocks along the allylic monomeric units as the result of isomerization of the double bonds (isomerization-induced light emission).
AB - We report the first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers via 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). The synthesized terpolymers possess a predictable molecular weight and monomodal low polydispersity (Mn, NMR=1.83-9.68×103 g /mol, Đ =1.09-1.22). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium ylide, affording well-defined terpolymers too (Mn, NMR=4.3-9.1×103 g/mol, Đ=1.16-1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as demonstrated by fluorescence and NMR spectroscopy. This phenomenon can be attributed to the formation of conjugated small blocks along the allylic monomeric units as the result of isomerization of the double bonds (isomerization-induced light emission).
UR - http://hdl.handle.net/10754/631513
UR - https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201901094
UR - http://www.scopus.com/inward/record.url?scp=85063808278&partnerID=8YFLogxK
U2 - 10.1002/anie.201901094
DO - 10.1002/anie.201901094
M3 - Article
C2 - 30807683
SN - 1433-7851
VL - 58
SP - 6295
EP - 6299
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
IS - 19
ER -