Star-Shaped Triphenylamine–Tetracyanobutadiene–Phenothiazine Push–Pull Systems: Role of Terminal Phenothiazine in Improving Charge Transfer

Yadav, Indresh Singh; Alsaleh, Ajyal Z.; Martin, Blake; Misra, Rajneesh; D’Souza, Francis

doi:10.1021/acs.jpcc.2c03495

Side chain alkyl groups have become the standard for incorporating solubilizing groups into conjugated polymers. However, the variety of alkyl groups available and their location on the polymer’s backbone can contribute to the packing of the polymer chains in many different ways, resulting in many different morphologies in the polymer that can affect its properties and performances. In this paper, we investigate the effects on the conductivity of nine phenothiazine-containing polyaniline derivatives (P1−P9) with alkyl or aryl side chains on the phenothiazine core while also varying the number of methyl groups on the p-phenylenediamine unit. 1H nuclear magnetic resonance spectroscopy, ultraviolet−visible spectroscopy, differential scanning calorimetry, scanning electron microscopy, atomic force microscopy, and wide-angle X-ray scattering (WAXS) were all used to study the polymers’ structures, physical and thermal properties, and morphologies. The t-butylphenyl substituent on the phenothiazine core seems to provide more rigidity in the polymer’s backbone resulting in higher Tg for series 3, while series 2 containing the 2-hexyldecyl-substituted polymers had the lowest Tg, which is attributed to the large volume of the side chain, that limits interchain interactions. Consequently, series 2 had the lowest conductivity. However, the strongest effect on the conductivity was seen from the tetramethyl groups on the PPDA unit, which resulted in the lowest conductivity in each series due to torsional strain (twisting) in the polymer’s backbone. The WAXS data suggest mostly amorphous films; thus, the conductivity in these materials seems to be dominated by a multiscale charge transport phenomenon that occurs in amorphous conjugated materials. Our results will aid in the understanding of side chain engineering of PANI derivatives for their optimum performances.

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