Spectroelectrochemistry of alternating ambipolar copolymers of 4,4′- and 2,2′-bipyridine isomers and quaterthiophene
PBN-AR
Instytucja
Instytut Chemii Organicznej Polskiej Akademii Nauk
Informacje podstawowe
Główny język publikacji
en
Czasopismo
Electrochimica Acta (40pkt w roku publikacji)
ISSN
0013-4686
EISSN
Wydawca
PERGAMON-ELSEVIER SCIENCE LTD
DOI
URL
Rok publikacji
2017
Numer zeszytu
Strony od-do
437 - 452
Numer tomu
231
Liczba arkuszy
Słowa kluczowe
en
Conjugated polymer
Bipyridine
Viologen
Thiophene
Push-pull systems
Polaron
Bipolaron
Streszczenia
Język
en
Treść
First report of π-conjugated push-pull copolymer systems with 4,4′-bipyridine moieties in the main macromolecular chain is presented. C-substitution pattern of electropolymerisable bithiophene pendants at the 4,4′-bipyridine unit offered the versatility to retain the latter as free amine, or convert it into bipyridylium salt. Both structures have been prepared and investigated, delivering the first example of a polymer with viologen unit making up the extended π-bond. Detailed electrochemical, spectroelectrochemical and quantum chemical study of these new polymer systems and their 2,2′-bipyridine analogues has shown that while linear structure and extended conjugation in the latter help it to accommodate charge carriers characteristic for heavily doped polythiophene, the conjugation break afforded by the meta substitution pattern across the 4,4′-pirydyl unit makes the polymer behave like an ensemble of shorter oligomeric segments with better defined electron transitions and sharper, and faster electrochromic response. Effective π-π interchain coupling between α,ω-bis(2-pyridyl)quaterthiophene repeating units was observed, whereas intramolecular interactions were found to dominate in the linear 2,2′-bipyridyl based polymer. While the bithiophene derivative of methyl viologen electropolymerised less easily than its corresponding non-quaternised derivative, the resulting polymer films demonstrated decent stability when subject to subsequent p- and n-doping, featuring pronounced charge trapping/detrapping signatures. Furthermore, ion pairing between the viologen and weakly basic PF6− and CF3SO3− counterions has been found to impact the redox chemistry of bithiophene functionalised viologen structure. Experimental findings have been confronted with results of quantum chemical computations helping to elucidate the electrochemical and spectroelectrochemical observations made. Presented study delivers insights into the doping processes taking place in conjugation disrupted 4,4'-bipyridine core copolymers, helping to evaluate their potential as substrates for new tuneable π-conjugated polymeric systems.
Cechy publikacji
discipline:Chemia
discipline:Chemistry
Original article
Original article presents the results of original research or experiment.
Oryginalny artykuł naukowy
Oryginalny artykuł naukowy przedstawia rezultaty oryginalnych badań naukowych lub eksperymentu.
Inne
System-identifier
PBN-R:828089
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