Mono and di-substituted BODIPY with electron donating carbazole, thiophene, and 3, 4-ethylenedioxythiophene units. (1st May 2018)

• Record Type: Journal Article
• Authors: Kurowska, Aleksandra; Brzeczek-Szafran, Alina; Zassowski, Pawel; Lapkowski, Mieczyslaw; Domagala, Wojciech; Wagner, Pawel; Wagner, Klaudia
• Is Part Of: Electrochimica acta. Volume 271(2018)
• Page Start: 685
• Page End: 698
• Publication Date: 2018-05-01
• Subjects: BODIPY -- Radical cation generation -- Spectroelectrochemistry -- Donor-acceptor; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2018.03.044
• Languages: English
• ISSNs: 0013-4686

Abstract

Abstract: In an effort to extend the conjugation system of boron-dipyrrin (BODIPY), the dye was coupled with polymerisable units of carbazole, alkylthiophene, and 3, 4-ethylenedioxythiophene (EDOT). Due to electron donating character of the units connected to the strong electron accepting segment of tri-coordinated boron, the optical and electrochemical properties of the dye changed, and followed the strength of the electron donating substituent. All studied compounds exhibited electroactivity in both anodic and cathodic potential ranges, however, electropolymerisation was only observed for BODIPY modified with EDOT, leading to trimeric and tetrameric substituents. Potential controlled optical changes (spectroelectrochemistry) and in situ spin density distribution measurements, supported by quantum chemical calculations using density functional theory, were undertaken in order to understand the reversibility of the electrochemical processes. Hyperfine split ESR spectra of the radical anion species were successfully modelled revealing intriguing, hyperconjugation type unpaired spin delocalisation patterns. Graphical abstract: