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 the ?-conjugated backbones that warrants for stabilization of the quasi-planar conformation of the polythiophene core and prevents electronic communication between adjacent chains. Thus, polythiophene-based insulated molecular wires (IMWs) constitute ideal test-beds to evaluate the structural changes within the conjugated polymer chain, such as intrachain conformation and ?-electron delocalization. Here, we investigate the structure and spectroscopic response of fully and partially insulated polythiophene-based IMWs. An experimental investigation of Raman spectra supported by density functional theory (DFT) calculations allows us to give a detailed interpretation of intramolecular interactions, highlighting differences in ?-electron conjugation revealed by the presence of an intensity transfer between the two main Raman modes associated with the C?C/C-C stretching vibrations. This study proves the sensitivity of Raman spectroscopy as a technique to monitor structural changes in self-encapsulated conjugated polymers.
CITATION STYLE
Mosca, S., Milani, A., Castiglioni, C., Hernández Jolín, V., Meseguer, C., López Navarrete, J. T., … Ruiz Delgado, M. C. (2022). Raman Fingerprints of ?-Electron Delocalization in Polythiophene-Based Insulated Molecular Wires. Macromolecules, 55(9), 3458–3468. https://doi.org/10.1021/acs.macromol.1c02458
Mendeley helps you to discover research relevant for your work.