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Electrochemical Synthesis and Electro-Optical Properties of Dibenzothiophene/Thiophene Conjugated Polymers With Stepwise Enhanced Conjugation Lengths.

ABSTRACT: A total of six conjugated polymers, namely PDBT-Th, PDBT-Th:Th, PDBT-2Th, PDBT-Th:2Th, PDBT-2Th:Th, and PDBT-2Th:2Th, consisting of dibenzothiophene, thiophene, and bithiophene were electrochemically synthesized. Their electrochemical and electrochromic properties were investigated in relation to the conjugation chain lengths of the thiophene units in the conjugated backbones. Density functional theory (DFT) calculations showed that longer conjugation lengths resulted in decreased HOMO-LUMO gaps in the polymers. The optical band gaps (E g,opt) and electrochemical band gaps (E g,cv) were decreased from PDBT-Th to PDBT-Th:Th, however, PDBT-Th:2Th, PDBT-2Th, PDBT-2Th:Th and PDBT-2Th:2Th displayed the similar band gaps. The conjugation length increments significantly improved the electrochemical stability of the conjugated polymers and exhibited reversible color changes due to the formation of polarons and bipolarons. The results suggest that the conjugated polymers prepared herein are promising candidates for fabricating flexible organic electrochromic devices.

SUBMITTER: Lin K

PROVIDER: S-EPMC7505771 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Electrochemical Synthesis and Electro-Optical Properties of Dibenzothiophene/Thiophene Conjugated Polymers With Stepwise Enhanced Conjugation Lengths.

Lin Kaiwen K Li Caiting C Tao Wang W Huang Jilong J Wu Qinghua Q Liu Zijin Z Zhang Yangfan Y Wang Da D Liu Xi X

Frontiers in chemistry 20200908

A total of six conjugated polymers, namely PDBT-Th, PDBT-Th:Th, PDBT-2Th, PDBT-Th:2Th, PDBT-2Th:Th, and PDBT-2Th:2Th, consisting of dibenzothiophene, thiophene, and bithiophene were electrochemically synthesized. Their electrochemical and electrochromic properties were investigated in relation to the conjugation chain lengths of the thiophene units in the conjugated backbones. Density functional theory (DFT) calculations showed that longer conjugation lengths resulted in decreased HOMO-LUMO gaps ...[more]

PMID: 33102439

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Project description:Pyrazinacenes are next generation N-heteroacenes and represent a novel class of stable n-type materials capable of accepting more than one electron and displaying intriguing features, including prototropism, halochromism, and redox chromism. Astonishingly, despite a century since their discovery, there have been no reports on the conjugated polymers of pyrazinacenes due to unknown substrate scope and lack of pyrazinacene monomers that are conducive to condensation polymerization. Breaking through these challenges, in this work, we report the synthesis of previously undiscovered and highly coveted conjugated polymers of pyrazinacenes. In order to understand the intricacies of conjugation extension within the acene and along the polymer backbone, a series of electronically diverse four pyrazinacene conjugated polymers were synthesized. Polymers synthesis required optimizing a few synthetic steps along the 12-step synthetic pathway. The generated pyrazinacene monomers are not amenable to the popular condensation polymerizations involving Pd or Cu catalysts. Gratifyingly, Pd and Cu free dehydrohalogenation polymerization of the monomer with HgCl2 resulted in high molecular weight organometallic conjugated pyrazinacene polymers within a few minutes at room temperature. The dual role played by the Hg(ii) during the polymerization, combined with the self-coupling of the RHgCl (intermediate), is at the core of successful polymerization. Notably, the self-coupling of intermediates challenges the strict stoichiometric balance typically required for step-growth polymerization and offers a novel synthetic strategy to generate high molecular weight conjugated polymers even with imbalanced monomer stoichiometries. A combination of electrochemical studies and DFT-B3LYP simulations indicated that the presence of the reduced pyrazine ring promotes interacene π-conjugation through the metal center, in contrast to completely oxidized tetrazaazaanthracene. The extension of conjugation results in ca. 2 eV lower reduction potential for polymers compared to the monomer, placing the LUMO energy levels of these polymers on par with some of the best-known n-type polymers. Also, the presence of NH protons in the pyrazinacene polymers show ionochromism and red-shift UV-vis absorption maximum by ca. 100 nm. This work not only shows a way to realize highly desirable and elusive pyrazinacene conjugated polymers but also paves the way for a library of n-type conjugated polymers that can undergo multi-electron reduction.

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Dataset Information

Electrochemical Synthesis and Electro-Optical Properties of Dibenzothiophene/Thiophene Conjugated Polymers With Stepwise Enhanced Conjugation Lengths.

Publications

Electrochemical Synthesis and Electro-Optical Properties of Dibenzothiophene/Thiophene Conjugated Polymers With Stepwise Enhanced Conjugation Lengths.

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