Topology and Ground State Control In Open-Shell Donor-Acceptor Conjugated Polymers

Authors

Kevin S. Mayer, University of Southern MississippiFollow
Daniel J. Adams, University of Southern MississippiFollow
Naresh Eedugurala, University of Southern MississippiFollow
Molly M. Lockart, The University of AlabamaFollow
Paramasivam Mahalingavelar, University of Southern MississippiFollow
Lifeng Huang, University of Southern Mississippi
Luke A. Galuska, University of Southern MississippiFollow
Eric R. King, University of Southern MississippiFollow
Xiaodan Gu, University of Southern MississippiFollow
Michael K. Bowman, The University of AlabamaFollow
Jason D. Azoulay, University of Southern MississippiFollow

Document Type

Article

Publication Date

6-23-2021

School

Polymer Science and Engineering

Abstract

Donor-acceptor (DA) conjugated polymers (CPs) with narrow bandgaps and open-shell (diradical) character represent an emerging class of materials whose rich behavior emanates from their collective electronic properties and diminished electron pairing. However, the structural and electronic heterogeneities that define these materials complicate bandgap control at low energies and connections linking topology, exchange interactions, and (opto)electronic functionality remain nascent. To address these challenges, we demonstrate structurally rigid and strongly π-conjugated copolymers comprised of a solubilizing thiadiazoloquinoxaline acceptor and cyclopenta[2,1-b:3,4-b′]dithiophene or dithieno[3,2-b:2′,3′-d]thiophene donors. Atom-specific substitution modulates local aromatic character within the donor resulting in dramatic differences in structural, physicochemical, electronic, and magnetic properties of the polymers. These long-range π-mediated interactions facilitate control between low-spin aromatic and high-spin quinoidal forms. This work provides a strategy to understand the evolution of the electronic structure within DA CPs, control the ground state spin multiplicity, tune spin-spin interactions, and articulate the emergence of their novel properties.

Comments

© Cell Reports Physical Science. Published version found at 10.1016/j.xcrp.2021.100467.

Publication Title

Cell Reports Physical Science

Volume

2

Issue

6

Recommended Citation

Mayer, K., Adams, D., Eedugurala, N., Lockart, M., Mahalingavelar, P., Huang, L., Galuska, L., King, E., Gu, X., Bowman, M., Azoulay, J. (2021). Topology and Ground State Control In Open-Shell Donor-Acceptor Conjugated Polymers. Cell Reports Physical Science, 2(6).
Available at: https://aquila.usm.edu/fac_pubs/18830