title: Tuning of electronic properties in thienyl-phosphole pi-conjugated systems through P-functionalization monitored by Raman spectroscopy.
abstract: Herein, a Raman spectroscopic study of a new family of 2,5-di(2-thienyl)phospholes and thienyl-capped 1,1'-diphospholes is presented. The Raman spectra have been carefully assigned with the help of density functional calculations. For di(2-thienyl)phospholes, two well-differentiated groups of Raman bands exist that arise either from the central phosphole ring or from the outer thiophene substituents. These data reveal a segmentation of the electronic structure. This paper reports interesting relationships between geometrical data such as the BLA (bond-length alternation) parameter and Raman band wavenumbers. These correlations are unprecedented in the chemistry of phospholes and have been used to interpret the evolution of the electronic structure (aromaticity=pi-conjugation) upon 1) substitution of the central sulfur atom of terthiophene by phosphorus and 2) P-functionalization. Increasing the coordination number of the phosphole ring results in intramolecular charge transfer. The best scenario for phosphole aromaticity is found for 1,1'-diphospholes.
authors.affiliation: Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain.
authors.forename: Juan
authors.initials: J
authors.lastname: Casado
authors.forename: Régis
authors.initials: R
authors.lastname: Réau
authors.forename: Juan T
authors.initials: JT
authors.lastname: López Navarrete