A Review on Self-Assembly Driven Optoelectronic Properties of Polythiophene-Peptide and Polythiophene-Polymer...

Polythiophene (PT) is an important conducting polymer for its outstanding optoelectronic properties. Here, we delineate the self-assembly-driven optoelectronic properties of PT-peptide and PT-polymer conjugates, taking examples from recent literature reports. PT-peptide conjugates made by both covalent and noncovalent approaches are discussed. Poly(3-thiophene acetic acid) (P3TAA) covalently coupled with Gly-Gly-His tripeptide, C-protected and deprotected tripeptide H₂N-F-F-V-OMe, etc. exhibits self-assembly-driven absorbance, fluorescence, photocurrent, and electronic properties. Noncovalent PT-peptide conjugates produced via ionic, H-bonding, and π-stacking interactions show tunable morphology and optoelectronic properties by varying the composition of a component. PT conjugated with Alzheimer's disease peptide (KLVFFAE, Aβ_16-22) shows enhanced photocatalytic water splitting, cationic PT(CPT-I)-perylene bisimide-appended dipeptide (PBI-DY), and anionic PT-perylene diimide-appended cationic peptide (PBI-NH₃⁺) conjugates and exhibits self-assembly-driven enhanced photoswitching and organic mixed electronic and ionic conductivity (OMEIC) properties. In the PT-polymer conjugates, self-assembly-driven optoelectronic properties of covalently produced PT-random copolymers, PT-block copolymers, PT-graft-random copolymers, and PT-graft-block copolymer conjugates are discussed. The HOMO-LUMO levels of hyperbranched polymers are optimized to obtain better power conversion efficiency (PCE) in the bulk heterojunction (BHJ) solar cell than in linear polymers, and P3TAA-ran-P3HT (43 mol % P3TAA) conjugated with MAPbI₃ perovskite exhibits higher PCE (10%) than that with only P3TAA hole-transporting material. In the ampholytic polythiophene (APT), on increasing pH, the morphology changes from the vesicle to fibrillar network for the dethreading of the PT chain, resulting in a red shift of the absorbance peak, an enormous increase in PL intensity, lowering of the charge transfer resistance, and an induction of Warburg impedance for the release of quencher I^- ions. The PT-g-(PDMAEMA-co-PGLU-HEM) graft copolymer self-assembles with Con-A lectin, causing fluorescence quenching, and acts as a sensor for Con-A with a LOD of 57 mg/L. Varying sequences of the block copolymer containing pH-responsive PDMAEMA and temperature-responsive PDEGMEM grafted to the PT backbone shows different self-assembly, optical, electronic, and photocurrent properties depending on the proximity and preponderance of the block sequence on the PT backbone.