TY - JOUR
T1 - Exploiting Visible-Light Induced Radical to Cation Transformation Pathway for Reactivity Enhanced Electrophilic Aromatic Substitution Polymerization of Heteroaromatics
AU - Gencosman, Emirhan
AU - Kiliclar, Huseyin Cem
AU - Fiedor, Pawel
AU - Yilmaz, Gorkem
AU - Ortyl, Joanna
AU - Yagci, Yusuf
AU - Kiskan, Baris
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2024/2
Y1 - 2024/2
N2 - A straightforward approach is employed to synthesize methylene-bridged poly(hetero aromatic)s based on furan, pyrrole, thiophene, and thiophene derivatives. The process involves an electrophilic aromatic substitution reaction facilitated by a visible light-initiated system consisting of manganese decacarbonyl and an iodonium salt. The approach mainly relies on the formation of halomethylium cation, the attack of this cation to heteroaromatic, regeneration of methylium cation on the heteroaromatic, and reactivity differences between halomethylium and heteroaromatic methylium cations for successful polymerizations. This innovative synthetic strategy lead to the formation of polymers with relatively high molecular weights as the stoichiometric imbalance between the comonomers increased. Accordingly, these newly obtained polymers exhibit remarkable fluorescence properties, even at excitation wavelengths as low as 330 nm. Moreover, by harnessing the halogens at chain ends of homopolymers, block copolymers are successfully synthesized, offering opportunities for tailored applications in diverse fields.
AB - A straightforward approach is employed to synthesize methylene-bridged poly(hetero aromatic)s based on furan, pyrrole, thiophene, and thiophene derivatives. The process involves an electrophilic aromatic substitution reaction facilitated by a visible light-initiated system consisting of manganese decacarbonyl and an iodonium salt. The approach mainly relies on the formation of halomethylium cation, the attack of this cation to heteroaromatic, regeneration of methylium cation on the heteroaromatic, and reactivity differences between halomethylium and heteroaromatic methylium cations for successful polymerizations. This innovative synthetic strategy lead to the formation of polymers with relatively high molecular weights as the stoichiometric imbalance between the comonomers increased. Accordingly, these newly obtained polymers exhibit remarkable fluorescence properties, even at excitation wavelengths as low as 330 nm. Moreover, by harnessing the halogens at chain ends of homopolymers, block copolymers are successfully synthesized, offering opportunities for tailored applications in diverse fields.
KW - electrophilic aromatic substitution
KW - manganese decacarbonyl
KW - onium salt
KW - photochemistry
KW - visible light-induced polymerization
UR - http://www.scopus.com/inward/record.url?scp=85178107194&partnerID=8YFLogxK
U2 - 10.1002/marc.202300458
DO - 10.1002/marc.202300458
M3 - Article
AN - SCOPUS:85178107194
SN - 1022-1336
VL - 45
JO - Macromolecular Rapid Communications
JF - Macromolecular Rapid Communications
IS - 3
M1 - 2300458
ER -