ThDione: A Powerful Electron‐Withdrawing Moiety for Push–Pull Molecules. Issue 7 (24th July 2020)

• Record Type: Journal Article
• Authors: Novotná, Eva; Kityk, Iwan V.; Pytela, Oldřich; Bureš, Filip; Ludwig, Miroslav; Klikar, Milan; Ozga, Katarzyna; Jedryka, Jaroslaw
• Is Part Of: ChemPlusChem. Volume 85:Issue 7(2020)
• Page Start: 1549
• Page End: 1558
• Publication Date: 2020-07-24
• Subjects: diones -- donor–acceptor systems -- electrochemistry -- (non)linear optics -- thiophenes; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202000395
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: A series of new push–pull chromophores based on a combined cyclopenta[ c ]thiophene‐4, 6‐dione (ThDione) acceptor, N, N ‐dimethylaniline, N ‐piperidinylthiophene or ferrocene donors, and ethylene or buta‐1, 3‐dienylene π‐linkers has been designed and synthesized. Utilizing one or two ThDione acceptors afforded linear or branched push–pull molecules. Experimental and theoretical study of their fundamental properties revealed thermal robustness up to 260 °C, a electrochemical/optical HOMO–LUMO gap that is tunable within the range of 1.47–2.19/1.99–2.39 eV, and thorough elucidation of structure–property relationships. Compared to currently available portfolio of heterocyclic electron‐withdrawing units, ThDione proved to be a powerful and versatile acceptor unit. It imparts significant intramolecular charge transfer and polarizes the π‐system, which results in enhanced (non)linear optical response. Abstract : A strong pull : ThDione, a π‐conjugated scaffold combining electron‐withdrawing cyclopenta‐1, 3‐dione and electron‐rich thiophene moieties, has been used as an electron acceptor in D‐π‐A systems. These compounds comprise either mesomeric or organometallic donors and various π‐linkers in order to systematically explore the intramolecular charge‐transfer behavior. The experimental and theoretical data revealed the superior properties of ThDione in terms of π‐system polarization.