2026-05-27T23:27:23Zhttps://riuma.uma.es/rest/oai/request

oai:riuma.uma.es:10630/246552026-02-03T11:12:25Zcom_10630_2254col_10630_37953

Mosca, Sara Milani, Alberto Castiglioni, Chiara Hernández-Jolín, Víctor Meseguer, Cristóbal López-Navarrete, Juan Teodomiro Zhao, Chunhui Sugiyasu, Kazunori Ruiz-Delgado, María del Carmen 2022-07-13T07:34:18Z 2022-07-13T07:34:18Z 2022-04-22 Mosca, Sara ; Milani, Alberto ; Castiglioni, Chiara ; Hernández-Jolín, Víctor ; Meseguer, Cristóbal ; López Navarrete, Juan T. ; Zhao, Chunhui ; Sugiyasu, Kazunori ; Ruíz-Delgado, María del Carmen. Macromolecules 2022, 55, 9, 3458–3468 Publication Date:April 22, 2022 https://doi.org/10.1021/acs.macromol.1c02458 https://hdl.handle.net/10630/24655 10.1021/acs.macromol.1c02458 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 π-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 π-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 π-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. eng http://creativecommons.org/licenses/by/4.0/ open access Atribución 4.0 Internacional Oligómeros (Polímeros) Raman Fingerprints of π-Electron Delocalization in Polythiophene-Based Insulated Molecular Wires journal article