The simple and elegant Buchwald-Hartwig cross-coupling reaction has been used to synthesise a designed range of new aniline-based tetramers in one step, and without the need for protecting groups. Variation of the central aromatic ring has provided the opportunity to carefully tune the optoelectronic properties in this series, thus enabling a structure-activity relationship study by using a range of photophysical and electrochemical techniques. As a result, the long-proposed sequences of electron-electron (EE) and electron-chemical (EC) processes that support the complex redox and proton-transfer reactions involved in the well-known switching of redox states of poly- and oligo(aniline)s are revealed here for the first time. We also present the initial results from time-dependent DFT calculations to clarify the optoelectronic behaviour of these oligomers. The dc-conductivity measurements of conducting thin films of this series, doped with the prototypical poly(aniline) protonating agent D,L-camphor-10-sulfonic acid (CSA), externally plasticised with triphenyl phosphate (TPP), and processed from m-cresol (MC) solutions, are also presented.
A tetra(aniline)-alkyl diblock compound was designed, synthesized and fully characterized. By employing suitable conditions, doped, electroactive microstructures could be prepared. The microstructures were characterized in detail and their anisotropic conductivity measured for the first time.
Well-designed BAB triblock copolymers with central polyether and flanking poly(lithium pentafluorostyrene sulfonate) blocks reach very high conductivities in the solid state.
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.
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