Tuning optical and electronic properties of poly(4,4'-triphenylamine vinylene)s by post-modification reactions

• Published in: Dyes and pigments 2015-02, Vol.113, p.227-238
• Main Authors: Grigoras, Mircea, Catargiu, Ana Maria, Ivan, Teofilia, Vacareanu, Loredana, Minaev, Boris, Stromylo, Evgeniy
• Format: Article
• Language: English
• Subjects: Chemical modification; Density functional theory; Density functional theory calculations; Dyes; Mathematical analysis; Monomers; Optical properties; Phenylethynyl and pyridylethynyl substituents; Polyarylenevinylenes; Spectra; Spectral methods; Synthesis; Tune optical and electrochemical properties; Tuning
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2014.08.016

New triphenylamine-based polyarylenevinylenes with pendant phenylethynyl- and 3-pyridylethynyl substituents were synthesized by Stille polycondensation of trans-1,2-bis(tributylstannyl)ethene with two new ethynyl substituted triphenylamine monomers, i.e., N,N-bis(4-iodophenyl)-4'-(phenylethynyl) phenylamine and N,N-bis(4-iodophenyl)-4'-(3-pyridylethynyl) phenylamine. The polymers were characterized by spectral methods and cyclic voltammetry and their properties were compared with those of the unsubstituted poly(4,4'-triphenylamine vinylene). Chemical post-modifications of the polymers by tetracyanoethylene addition to the triple bond, and quaternization of pyridyl group with accent on the fine-tuning of the optical and electrochemical properties were also studied. Density functional theory calculations provide a reliable interpretation of the observed spectra and electrochemical data. [Display omitted] •Polyarylenevinylenes with phenylethynyl and pyridylethynyl side groups were prepared.•Chemical modification of triple bond was performed with tetracyanoethylene.•Chemical modification of pyridine ring was performed by alkylation and protonation.•Optical and electronic properties of polymers were studied after chemical post-modification.