Symmetrically Disubstituted Bithiophene Derivatives of 1,3,4-Oxadiazole, 1,3,4-Thiadiazole, and 1,2,4-Triazole – Spectroscopic, Electrochemical, and Spectroelectrochemical Properties

Symmetrically Disubstituted Bithiophene Derivatives of 1,3,4-Oxadiazole, 1,3,4-Thiadiazole, and 1,2,4-Triazole – Spectroscopic, Electrochemical, and Spectroelectrochemical Properties Full article

Journal

Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2014, Volume: 118, Number: 43, Pages: 25176-25189 Pages count : 14 DOI: 10.1021/jp507838c

Authors

Kurowska Aleksandra ¹ , Kostyuchenko Anastasia S. ^2,3 , Zassowski Pawel ¹ , Skorka Lukasz ⁴ , Yurpalov Viacheslav L. ² , Fisyuk Alexander S. ^2,3 , Pron Adam ⁴ , Domagala Wojciech ¹

Affiliations

1	Department of Physical Chemistry and Technology of Polymers, Silesian University of Technology
2	Department of Organic Chemistry, Omsk F. M. Dostoevsky State University
3	Laboratory of New Organic Materials, Omsk State Technical University
4	Faculty of Chemistry, Warsaw University of Technology

Electrochemical and spectroelectrochemical properties of a series of new penta-ring donor−acceptor compounds, comprising 1,3,4-oxadiazole, 1,3,4-thiadiazole, and 1,2,4-triazole central ring, symmetrically connected to substituted bithiophenes, were investigated. Aromaticity and electrophilic−nucleophilic traits of the aza-heterocyclic units, fostering inductive and resonance effects that translate to conjugation enhancement and electron (de)localization, were found a major factor determining the key electron properties of ionization potential (IP) and electron affinity (EA) of these molecules. Replacing the alkyl thiophene substituent for an alkoxy one afforded certain control over the two parameters as well. All studied compounds were found to undergo electrochemical polymerization giving p- and n-dopable products, featuring good electrochemical reversibility of their oxidative doping process, as demonstrated by cyclic voltammetry and UV−vis−NIR, EPR spectroelectrochemistry. While electropolymerization of entities differing in the heterodiazole unit was found to conserve the EA value, the IP parameter of polymerization products was found to decrease by 0.6−0.7 eV, affording an asymmetric narrowing of the frontier energy levels gap. Aided by quantum chemical computations, the effects of structure tailoring of the investigated systems are rationalized, pointing to conscious ways of shaping the electronic properties of thiophene class polymers using synthetically convenient heterodiazole π-conjugated units.

Kurowska A. , Kostyuchenko A.S. , Zassowski P. , Skorka L. , Yurpalov V.L. , Fisyuk A.S. , Pron A. , Domagala W.
Symmetrically Disubstituted Bithiophene Derivatives of 1,3,4-Oxadiazole, 1,3,4-Thiadiazole, and 1,2,4-Triazole – Spectroscopic, Electrochemical, and Spectroelectrochemical Properties

Journal of Physical Chemistry C. 2014. V.118. N43. P.25176-25189. DOI: 10.1021/jp507838c WOS Scopus РИНЦ OpenAlex

Full text from publisher

Submitted:	Aug 3, 2014
Accepted:	Oct 1, 2014
Published print:	Oct 17, 2014
Published online:	Oct 17, 2014

Web of science:	WOS:000344135500044
Scopus:	2-s2.0-84949116422
Elibrary:	23997880
OpenAlex:	W2323999038

DB	Citing
Scopus	38
Web of science	34
OpenAlex	39