Tipping the polaron-bipolaron balance: concentration and spin effects in doped oligo(aniline)s observed by UV-vis-NIR and TD-DFTElectronic supplementary information (ESI) available: Instrumentation, experimental details, DFT-calculated structures, charge distributions, frontier molecular orbitals, experimental and simulated UV-vis-NIR spectra, ESR spectra, analysis of computational method effects, Cartesian coordinates of computed molecular structures. CCDC 1562964. For ESI and crystallographic

• Main Authors: Mills, Benjamin M, Shao, Zhecheng, Flynn, Stephanie R, Rannou, Patrice, Lindsay, David M, Fey, Natalie, Faul, Charl F. J
• Format: Journal Article
• Published: 11.02.2019
• ISSN: 2058-9689
• DOI: 10.1039/c8me00082d

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 protonic 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. Computational and experimental study of UV-vis-NIR spectra, highlighting that doped oligo(aniline)s form mixtures of polaronic and bipolaronic spin isomers in solution.