Chirality in polythiophenes: A review

Abstract

Chiroptical polythiophene (PTh), as one of the most important chiral conductive polymers, is an emerging and hot topic in chiral materials, which shows great application potentials in fields as diverse as chiral sensing and separation, asymmetry catalysis, chiroptoelectronics, and even chirospintronics. This review summarizes progress in chiral polythiophenes (PThs) in the past 10 years, including the synthesis, properties and applications. Main focus is placed on the manner in which chirality is implemented and the optical activity of the chiral PThs. We showcase examples in which the chirality of PThs is induced by side chain substituents with point, planar, and axial chirality or arises from external chiral media. Application of chiral PThs is also included. Finally, perspectives for further development are offered.

Influence of the dispersity and molar mass distribution of conjugated polymers on the aggregation type and subsequent chiral expression

“…ECD measurements are commonly employed in chiral CPs and here utilized to impartially and straightforwardly determine the correct aggregation type of the solution. [53][54][55][56][57] Specifically, type I aggregation has a more effective long range interaction due to closer interlamellar distances and stronger p-stacking, leading to an additional monosignate Cotton effect. Contrarily, a symmetrical bisignate Cotton effect is expected in type II as the interactions are mostly governed by the The dotted lines represent the maximum molar mass where the elution curves reach zero.…”

Introducing Molecular Asymmetry in Copolymer Structures to Favor Herringbone-Like Aggregation and Tune the Chiral Expression

“…For the homopolymers, type I is obtained in both cases, comparable to previous reports. ,, This is determined based on the shape of the UV–vis spectra, wherein the 0–0 transition related to π–π stacking at high wavelength (low energy) is very pronounced in both cases (Figure ). Furthermore, this transition occurs at 625 nm (1.98 eV) for P1 and 604 nm (2.05 eV) for P2 , values corresponding to type I in branched, chiral P3AT and linear, achiral P3AT, respectively. , For the chiral P1 , there is a bisignate Cotton effect present as a result of exciton coupling and Davydov splitting between the neighboring chromophores. − Due to the angular momentum between these chromophores, they yield two similar but opposite signals. − A strong monosignate Cotton effect at 635 nm (1.95 eV) as a result of long-range helicity is simultaneously present, giving rise to the very clear and typical asymmetrical shape of the ECD spectra as a result of the formation of type I aggregates…”

Polymer‐Based Circularly Polarized Luminescent Materials

“…Polythiophenes are regarded as attractive π-conjugated polymers for the construction of CPL emitters due to their profound optoelectronic properties. [111][112][113] For example, Akagi and coworkers fabricated a series of thiophene-based fluorescence polymers bearing chiral nonyloxy carbonyl pendant, most of which could exhibit main-chain liquid crystallinity properties. [114] The obtained polythiophene derivatives showed RGBcolored fluorescence and CPL in solution and film.…”