Exploiting Visible-Light Induced Radical to Cation Transformation Pathway for Reactivity Enhanced Electrophilic Aromatic Substitution Polymerization of Heteroaromatics


Gencosman E., Kılıçlar H. C., Fiedor P., Yılmaz A. G., Ortyl J., Yağcı Y., ...More

Macromolecular Rapid Communications, vol.45, no.3, 2024 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 45 Issue: 3
  • Publication Date: 2024
  • Doi Number: 10.1002/marc.202300458
  • Journal Name: Macromolecular Rapid Communications
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Aerospace Database, Agricultural & Environmental Science Database, Applied Science & Technology Source, Chemical Abstracts Core, Chimica, Communication Abstracts, Compendex, INSPEC, MEDLINE, Metadex, Civil Engineering Abstracts
  • Keywords: electrophilic aromatic substitution, manganese decacarbonyl, onium salt, photochemistry, visible light-induced polymerization
  • Istanbul Technical University Affiliated: Yes

Abstract

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.