University of Southern Mississippi, Hattiesburg, MS (United States); School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, MS 39406, USA.
University of Southern Mississippi, Hattiesburg, MS (United States)
University of Alabama, Tuscaloosa, AL (United States)
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.
Mayer, Kevin S., et al. "Topology and ground state control in open-shell donor-acceptor conjugated polymers." Cell Reports Physical Science, vol. 2, no. 6, Jun. 2021. https://doi.org/10.1016/j.xcrp.2021.100467
Mayer, Kevin S., Adams, Daniel J., Eedugurala, Naresh, Lockart, Molly M., Mahalingavelar, Paramasivam, Huang, Lifeng, Galuska, Luke A., King, Eric R., Gu, Xiaodan, Bowman, Michael K., & Azoulay, Jason D. (2021). Topology and ground state control in open-shell donor-acceptor conjugated polymers. Cell Reports Physical Science, 2(6). https://doi.org/10.1016/j.xcrp.2021.100467
Mayer, Kevin S., Adams, Daniel J., Eedugurala, Naresh, et al., "Topology and ground state control in open-shell donor-acceptor conjugated polymers," Cell Reports Physical Science 2, no. 6 (2021), https://doi.org/10.1016/j.xcrp.2021.100467
@article{osti_1985337,
author = {Mayer, Kevin S. and Adams, Daniel J. and Eedugurala, Naresh and Lockart, Molly M. and Mahalingavelar, Paramasivam and Huang, Lifeng and Galuska, Luke A. and King, Eric R. and Gu, Xiaodan and Bowman, Michael K. and others},
title = {Topology and ground state control in open-shell donor-acceptor conjugated polymers},
annote = {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.},
doi = {10.1016/j.xcrp.2021.100467},
url = {https://www.osti.gov/biblio/1985337},
journal = {Cell Reports Physical Science},
issn = {ISSN 2666-3864},
number = {6},
volume = {2},
place = {United States},
publisher = {Elsevier},
year = {2021},
month = {06}}
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 214, Issue 1119, p. 451-465https://doi.org/10.1098/rspa.1952.0181