Electronic and Magnetic Properties of Oligomers and Chains of Poly(benzodifurandione) (PBDF), A Highly Conducting n-Type Polymer
- University of Arizona, Tucson, AZ (United States); University of Arizona
- University of Arizona, Tucson, AZ (United States)
The seminal development of highly electrically conducting polyacetylene via oxidative or reductive treatment (“doping”) has continuously inspired the search for other conducting π-conjugated polymers. Recently, poly(benzodifurandione), PBDF, was reported to have unexpected solubility given the absence of side chains and to exhibit an unprecedented, high electrical conductivity upon reduction (“n-doping”), with protons acting as counterions. Here, we theoretically investigate the electronic and magnetic properties of PBDF by taking long oligomers and one-dimensional (1D) periodic chains as model systems. With the oligomer models, we characterize the formation of polarons and bipolarons in n-doped PBDF. Our results indicate that singlet bipolarons tend to be the energetically most favorable species when protons bind to two closely located carbonyl groups in nearest-neighbor benzodifurandione moieties. The calculations on the 1D periodic chain models show that the positions of the protonated carbonyl groups determine the metallic, semiconducting, or insulating nature of a PBDF chain. When the protonated carbonyl groups are all situated on the same side of a PBDF chain, a stable helical chain configuration is found that exhibits ferromagnetic behavior. Our findings elucidate the mechanism of polaron and bipolaron formation in long oligomers of n-doped PBDF and highlight the fascinating electronic and magnetic properties of periodic 1D chains. Furthermore, these studies also provide a stepping stone for investigations of PBDF thin films, for which two- and three-dimensional structures must be considered.
- Research Organization:
- University of Arizona, Tucson, AZ (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0023411
- OSTI ID:
- 1996008
- Journal Information:
- Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 15 Vol. 35; ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English