Search

This work investigates the evolution of the molecular, vibrational, and optical properties within a family of carbonyl-functionalized quaterthiophenes: 5,5'''-diheptanoyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (2), and 2,7-[bis(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophene-4-one (3). The analysis is performed by Raman and UV/Vis absorption/excitation/fluorescence spectroscopy in combination with density functional calculations. Theoretical calculations show that substitution with carbonyl groups and perfluorohexyl chains induces progressive quinoidization of the π-conjugated backbone in comparison to the carbonyl-free compound 5,5'''-dimethyl-2,2':5',2'':5'',2'''-quaterthiophene (DM-4T) used as reference. Raman spectra are dominated by a strong Raman line which mainly corresponds to a combination of C-C/C=C stretching vibrations spreading over the whole thiophene core. This band undergoes a remarkable downshift as a consequence of the structural changes induced by the electron-withdrawing groups on the π-conjugated backbone. The band splitting on incorporation of a central carbonyl bridge evidences the formation of two structural domains in the molecule. The excitation and fluorescence spectra recorded at low temperature show well-resolved vibronic structures associated with the most intense collective C-C/C=C stretching mode. Optical absorption and fluorescence bands exhibit remarkable bathochromic dispersion on carbonyl functionalization, indicative of extension of π conjugation. TDDFT calculations enable a detailed description of the trends observed in the absorption spectra. Resonance Raman spectra reflect the structural changes predicted for the S(0)→S(1) electronic transition and evidence the cross-conjugated character that the central carbonyl group confers on 3., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, we study the pi-conjugational properties of a homologous series of all-anti oligothienoacenes containing four to eight fused thiophene rings by means of FT Raman spectroscopy and DFT calculations. The theoretical analysis of the spectroscopic data provides evidence that selective enhancement of a very limited number of Raman scatterings is related to the occurrence in these oligothienoacenes of strong vibronic coupling between collective nu(C=C) stretching modes in the 1600-1300 cm(-1) region and the HOMO/LUMO frontier orbitals (HOMO=highest occupied molecular orbital; LUMO=lowest unoccupied molecular orbital). The correlation of the Raman spectroscopic data and theoretical results for these all-anti oligothienoacenes with those previously collected for a number of all-syn oligothienohelicenes gives further support to the expectation that cross-conjugation is dominant in heterohelicenes. Fully planar all-anti oligothienoacenes display linear pi conjugation which seemingly does not reach saturation with increasing number of annulated thiophene rings in the oligomeric chain at least up to the octamer.

The UV/Vis, infrared absorption, and Raman scattering spectra of 3',4'-dibutyl-5,5"-bis(dicyanomethylene)-5,5"-dihydro-2,2':5',2"-terthiophene have been analyzed with the aid of density functional theory calculations. The compound exhibits a quinoid structure in its ground electronic state and presents an intramolecular charge transfer from the terthiophene moiety to the C(CN)2 groups. The molecular system therefore consists of an electron-deficient terthiophene backbone end-capped with electron-rich C(CN)2 groups. The molecule is characterized by a strong absorption in the red, due to the HOMO-->LUMO pi-pi* electronic transition of the terthiophene backbone that shifts hypsochromically on passing from the solid state to solution and with the polarity of the solvent. The analysis of the vibrational spectra confirms the structural conclusions and supports the existence of an intramolecular charge transfer. Vibrational spectra in several solvents and as a function of temperature have also been studied. Significant frequency upshifts of the vibrations involved in the pi-electron-conjugated pathway have been noticed upon solution in polar solvents and with the lowering of the temperature. Finally, we propose a quinoid molecule as a reliable structural and electronic model for dication species in doped oligothiophenes or for bipolaron charged defects in doped polythiophene.