Jump to main content
Jump to site search


Tipping the polaron–bipolaron balance: concentration and spin effects in doped oligo(aniline)s observed by UV-vis-NIR and TD DFT

Abstract

The oxidation states and doped forms of oligo(aniline)s are readily interconverted, and each state has characteristic UV vis NIR absorptions, making this spectroscopic technique ideal for in situ analysis of oligo(aniline) behaviour. However, experimental isolation of some of these states can be challenging and quantitative agreement between experimental and calculated spectra has been poor, making it difficult to identify the exact structure(s) and properties of each state. Here we report a comprehensive study of the UV-vis-NIR spectra of all oxidation states and doped forms of a series of oligo(aniline)s of varying lengths (dimer, tetramer and octamer), using a computationally inexpensive DFT method that is particularly suited to molecules with charge-transfer character. The computational study suggests that doped oligo(aniline)s form mixtures of spin isomers (polaronic and bipolaronic forms) in solution, and we have been able to evaluate and compare the most likely electronic configurations, as well as supporting our insights experimentally, by ESR spectroscopy. This doping approach enables tuning of the spin isomer equilibrium position by varying the concentration of acid dopant, offering a new pathway to explore the electronic structure of π-conjugated molecules more generally, and opening up new approaches to the design of spintronic materials.

Back to tab navigation

Supplementary files

Publication details

The article was received on 31 Oct 2018, accepted on 03 Dec 2018 and first published on 04 Dec 2018


Article type: Paper
DOI: 10.1039/C8ME00082D
Citation: Mol. Syst. Des. Eng., 2018, Accepted Manuscript
  •   Request permissions

    Tipping the polaron–bipolaron balance: concentration and spin effects in doped oligo(aniline)s observed by UV-vis-NIR and TD DFT

    B. M. Mills, Z. Shao, S. R. Flynn, P. Rannou, D. M. Lindsay, N. Fey and C. F. Faul, Mol. Syst. Des. Eng., 2018, Accepted Manuscript , DOI: 10.1039/C8ME00082D

Search articles by author

Spotlight

Advertisements