Quinonoid versus Aromatic π-Conjugated Oligomers and Polymers and Their Diradical Characters

Grover, Girishma; Tovar, John D.; Kertesz, Miklos

doi:10.1021/acs.jpcc.2c00113

Quinonoid versus Aromatic π-Conjugated Oligomers and Polymers and Their Diradical Characters

Journal Article · Mon Mar 14 00:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c00113· OSTI ID:1864954

Grover, Girishma ^[1]; ^[2]; ^[3]

Georgetown Univ., Washington, DC (United States); Georgetown University, Chemistry Department
Johns Hopkins Univ., Baltimore, MD (United States)
Georgetown Univ., Washington, DC (United States)

Quinonoid elements in π-conjugated oligomers and polymers have promising characteristics by providing unique structures and electronic properties, including varying degrees of ground state open shell diradical character and small band gaps. So far, quinonoid ground state polymers were rarely identified, and one of the goals of this work was to expand the portfolio of such systems in which over 17 different repeat units were considered, about half preferred a quinonoid and half preferred aromatic structures plus several with the alternating A-Q composition were also included. The dependency of the diradical character as a function of size and composition opens a rich space to discover trends affecting the aromaticity and diradical character. Herein, we show that the diradical character is a useful parameter to classify a wide variety of polymers based on their ground states in a systematic study of a large number of homo- and heterosystems. Homo-polymers with quinonoid ground states show a high diradical character, while those with the aromatic ground state behave as closed-shell systems with no or a very small diradical character. The diradical character of quinonoid systems depends strongly on the size, which increases with the size of the oligomer. Here, we found a correlation between the diradical character and the interring C–C distance as well as the singlet–triplet energy gaps. In alternating copolymers mixing quinonoid and aromatic subunits, we found open-shell hetero-polymers with moderate to high diradical characters.

View Accepted Manuscript (DOE)

Research Organization:: Georgetown Univ., Washington, DC (United States); Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019017

OSTI ID:: 1864954

Alternate ID(s):: OSTI ID: 1906718

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 11 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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