Strong Acceptor Annulation Enables Control of Electronic Structure and Spin Configuration In Donor-Acceptor Conjugated Polymers

Authors

Naresh Eedugurala, University of Southern MississippiFollow
Michael E. Steelman, University of Southern MississippiFollow
Paramasivam Mahalingavelar, University of Southern MississippiFollow
Daniel J. Adams, University of Southern MississippiFollow
Kevin S. Mayer, University of Southern MississippiFollow
Chih-Ting Liu, University of Southern MississippiFollow
Anthony Benasco, University of Southern MississippiFollow
Guorong Ma, University of Souhern MississippiFollow
Xiaodan Gu, University of Southern MississippiFollow
Michael K. Bowman, University of AlabamaFollow
Jason D. Azoulay, University of Southern MississippiFollow

Document Type

Article

Publication Date

4-5-2023

School

Polymer Science and Engineering

Abstract

Open-shell conjugated polymers (CPs) offer new opportunities to integrate the spin degree of freedom within emerging technologies. Central to their realization are strong acceptors that stabilize unpaired spins within the π-conjugated backbones. Here, we demonstrate a high-spin CP composed of alternating benzo[1,2-b:4,5-b′]dithiophene donors and a new, strongly electron-withdrawing 6,7,8,9-tetrachloro-[1,2,5]thiadiazolo[3,4-b]phenazine acceptor. A comparative study with a 6,7-dimethyl-[1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ) acceptor demonstrates that annulation and chlorination of the TQ framework facilitates a transition between closed-shell aromatic and high-spin quinoidal forms. This is accompanied by a concomitant reduction of the bandgap, high electron affinity, delocalization of spin density, and n-type conduction. These insights enable access to a broader range of open-shell CPs and the manipulation of important properties such as topology, exchange interactions, and carrier polarity.

Publication Title

Chemistry of Materials

Volume

35

Issue

8

First Page

3115

Last Page

3123

Recommended Citation

Eedugurala, N., Steelman, M. E., Mahalingavelar, P., Adams, D. J., Mayer, K. S., Liu, C., Benasco, A., Ma, G., Gu, X., Bowman, M. K., Azoulay, J. D. (2023). Strong Acceptor Annulation Enables Control of Electronic Structure and Spin Configuration In Donor-Acceptor Conjugated Polymers. Chemistry of Materials, 35(8), 3115-3123.
Available at: https://aquila.usm.edu/fac_pubs/20999