Terpolymers from Borane‐Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission

Abstract

The first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene,[ (C1-co-C3)b-C1],t erpolymers was achieved by one-pot borane-initiated random copolymerization of w-methylallyl (C3 units,c hain is growing by three carbon atoms at at ime) and benzyltriphenylarsonium (C1 units,chain is growing by one carbon atom at at ime) ylides,f ollowed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides,s uch as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well-defined, possess ap redictable molecular weight and low polydispersity (M n,NMR = 1.83-9.68 10 3 gmol À1 , = 1. 09-1.22). An unexpected light emission phenomenon was discoveredi nt hese non-conjugated terpolymers,asconfirmed 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).

Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units

“…Although challenging to synthesize, C3-polymers have unique and interesting properties, as reported by our group . An unexpected light emission phenomenon was observed and reported for the first time from a nonconjugated C3 polymer, poly­(3-methyl-propenylidene) (P3-MeAY), either in solution or in bulk, due to the isomerization-induced emission .…”

“…Model PE-based polymers, such as block, star, , comb-shaped, , or even tadpole-shaped, were obtained and used in thermodynamic studies by combining C1 polymerization with other living or living/controlled polymerizations. On the other hand, the polymerization of allylic arsonium ylides is a relatively new area that leads to unique structures. − These polymers have backbones where the double bonds are separated by a single carbon and not by two, as in 1,4-polyisoprene or 1,4-polybutadiene. Methyl-substituted and unsubstituted allylic arsonium ylides have been used to synthesize C3 polymers, where the double bond substitution pattern has had a striking impact on the product .…”

“…Although challenging to synthesize, C3-polymers have unique and interesting properties, as reported by our group. 16 An unexpected light emission phenomenon was observed and reported for the first time from a nonconjugated C3 polymer, poly(3-methyl-propenylidene) (P3-MeAY), either in solution or in bulk, due to the isomerization-induced emission. 14 Recently, fluorescent polymers have attracted considerable attention due to their unique application in OLED devices, 19 bioimaging, 20,21 explosive detection, 22−24 discoveries, it is desirable to have novel polymers with adjustable structures.…”

High trans-Selectivity in Boron-Catalyzed Polymerization of Allylic Arsonium Ylide and its Contribution to Thermal Properties of C3-Polymers

“…This unique structure has the potential of unique properties, such as light emission from a nonconjugated C3-chain due to the isomerization-induced phenomenon. 19 Although the boron-catalyzed polymerization of allylic arsonium ylide can offer unique C3-polymers, definitive confirmation of the mechanism has not been found yet. It is mostly because of the high polymerization ratio (completion within seconds) and instability of the allylic arsonium ylides.…”

“…Thanks to those copolymers with well-defined polymethylene block(s), some basic properties have been studied, such as crystallinity and aggregation. , Besides, well-defined (co)­brush macromolecules containing polymethylene blocks were synthesized, and their thermodynamic properties were studied. , The C3-polymers, hardly obtained using traditional polymerization techniques, have an unsaturated backbone, where the double bonds are separated by only one methylene carbon atom and not by two as in the case of 1,4-polyisoprene or 1,4-butadiene. This unique structure has the potential of unique properties, such as light emission from a nonconjugated C3-chain due to the isomerization-induced phenomenon …”