D‑A‑D Compounds Combining Dithienopyrrole Donors and Acceptors of Increasing Electron-Withdrawing Capability: Synthesis, Spectroscopy, Electropolymerization, and Electrochromism

Five D-π-A-π-D compounds consisting of the same donor unit (dithieno[3,2-b:2′,3′-d]pyrrole, DTP), the same π-linker (2,5-thienylene), and different acceptors of increasing electron-withdrawing ability (1,3,4-thiadiazole (TD), benzo[c][1,2,5]thiadiazole (BTD), 2,5-dihydropyrrolo[3,4-c]pyrrole-...

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Bibliographic Details
Published in:	The journal of physical chemistry. B Vol. 126; no. 22; pp. 4089 - 4105
Main Authors:	Rybakiewicz-Sekita, Renata, Toman, Petr, Ganczarczyk, Roman, Drapala, Jakub, Ledwon, Przemyslaw, Banasiewicz, Marzena, Skorka, Lukasz, Matyjasiak, Anna, Zagorska, Malgorzata, Pron, Adam
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 09-06-2022
Subjects:	B: Liquids; Chemical and Dynamical Processes in Solution
Online Access:	Get full text
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Summary:	Five D-π-A-π-D compounds consisting of the same donor unit (dithieno[3,2-b:2′,3′-d]pyrrole, DTP), the same π-linker (2,5-thienylene), and different acceptors of increasing electron-withdrawing ability (1,3,4-thiadiazole (TD), benzo[c][1,2,5]thiadiazole (BTD), 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP), 1,2,4,5-tetrazine (TZ), and benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NDI)) were synthesized. DTP-TD, DTP-BTD, and DTP-DPP turned out to be interesting luminophores emitting either yellow (DTP-TD) or near-infrared (DTP-BTD and DTP-DPP) radiation in dichloromethane solutions. The emission bands were increasingly bathochromically shifted with increasing solvent polarity. Electrochemically determined electron affinities (\|EA\|s) were found to be strongly dependent on the nature of the acceptor changing from 2.86 to 3.84 eV for DTP-TD and DTP-NDI, respectively, while the ionization potential (IP) values varied only weakly. Experimental findings were strongly supported by theoretical calculations, which correctly predicted the observed solvent dependence of the emission spectra. Similarly, the calculated IP and EA values were in excellent agreement with the experiment. DTP-TD, DTP-BTD, DTP-TZ, and DTP-NDI could be electropolymerized to yield polymers of very narrow electrochemical band gap and characterized by redox states differing in color coordinates and lightness. Poly(DTP-NDI) and poly(DTP-TD) showed promising electrochromic behavior, not only providing a rich color palette in the visible but also exhibiting near-infrared (NIR) electrochromism.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	1520-6106 1520-5207 1520-5207
DOI:	10.1021/acs.jpcb.2c01772