Abstract Poly(thienylene vinylene)s (PTV's) are early examples of conjugated polymers but have not been extensively studied when compared with closely analogous polythiophenes. PTV's synthesized through previously reported techniques are similar in structures that contain various alkyl or alkoxy side‐chains that exert limited impact on the polymer electronic properties. Herein, we report the preparation of a series of regio‐regular PTV's (rr‐PTV's) bearing cross‐conjugated side‐chains through ADMET polymerization of a common brominated di(thienylene vinylene) (DTV) monomer followed by PPM reactions on the resulting brominated PTV. These new polymers contain a bulky silyloxy alkyl side‐chain and a functionalized thiophene moiety on every main‐chain thiophene unit, and their regio‐regular placement is confirmed by NMR spectroscopy. The thienyl based side‐groups broaden polymer absorption ranges and at the same time lead to uncommon emission properties that are results of light‐induced charge transfer events between the polymer main‐chains and side‐chains. Removal of the silyl groups on one of these rr‐PTV's led to insoluble materials and x‐ray diffraction experiments on the collected solids displayed distinct scattering peaks that are absent from similarly functionalized regio‐random PTV's reported previously, thus suggesting better crystallinity originated from regio‐regularity.
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Side Chain Effects on the Conductivity of Phenothiazine-Derived Polyaniline
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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- Award ID(s):
- 1945503
- PAR ID:
- 10497659
- Publisher / Repository:
- pubs.acs.org/cm
- Date Published:
- Journal Name:
- Chemistry of materials
- ISSN:
- 0897-4756
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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