Raman Fingerprints of ?-Electron Delocalization in Polythiophene-Based Insulated Molecular Wires

Insulated polythiophenes with a polyrotaxane-like 3D architecture have shown excellent intrawire hole mobility, allowing their use in interesting optoelectronic applications. This is due to the isolation of ?-conjugated backbones that warrants for stabilization quasi-planar conformation polythiophene core and prevents electronic communication between adjacent chains. Thus, polythiophene-based insulated molecular wires (IMWs) constitute ideal test-beds evaluate structural changes within conjugated polymer chain, such as intrachain ?-electron delocalization. Here, we investigate structure spectroscopic response fully partially IMWs. An experimental investigation Raman spectra supported by density functional theory (DFT) calculations allows us give detailed interpretation intramolecular interactions, highlighting differences conjugation revealed presence an intensity transfer two main modes associated C?C/C–C stretching vibrations. study proves sensitivity spectroscopy technique monitor self-encapsulated polymers.