Thermochromism in polyalkylthiophenes: Molecular aspects from vibrational spectroscopy

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Abstract
It is known that polyalkylthiophenes show reversible thermochromism within a well-defined temperature range. The vibrational infrared and Raman spectra are used as structural probes for understanding the structures of polyhexyl and polyoctyl thiophenes at room temperature and their evolution with temperature during the thermochromic process. The seemingly sample IR and Raman spectra of these materials are explained in terms of the theory of the effective conjugation coordinate which also accounts for the observed ‘‘dispersion’’ of the Raman spectrum with exciting wavelength or from solid to solution states in terms of changes of effective conjugation length. A detailed description of the structure of the system is reached. At room T the sample consists mainly of two phases: (i) an ordered phase with the alkyl side chains in the transplanar structure and the main chain in a quasicoplanar or coplanar conformation and (ii) a disordered phase with the alkyl residue fully conformationally coiled and the main chain conformationally twisted with the torsional angle of ∼ 30°. Upon heating, the relative concentration of the disordered phase increases. The temperature dependence of the side chain and the main chain conformations are similar, thus showing that the coiling of the side chain drives the twisting of the main chain. The thermochromism is thus accounted for.