title: Comparison of thiophene-pyrrole oligomers with oligothiophenes: a joint experimental and theoretical investigation of their structural and spectroscopic properties.
abstract: We have prepared a new series of mixed thiophene-pyrrole oligomers to investigate the electronic benefits arising from the combination of these two heterocycles. The oligomers are functionalized with several hexyl and aryl groups to improve both processability and chemical robustness. An analysis of their spectroscopic (absorption and emission), photophysical, electrochemical, solid state, and vibrational properties is performed in combination with quantum-chemical calculations. This analysis provides relevant information regarding the use of these materials as organic semiconductors. The balance between the high aromatic character of pyrrole and the moderate aromaticity of thiophene allows us to address the impact of the coupling of these heterocycles in conjugated systems. The data are interpreted on the basis of the aromaticity, molecular conformations, ground and excited electronic state structures, frontier orbital topologies and energies, oxidative states, and quinoidal versus aromatic competition.
authors.affiliation: Department of Physical Chemistry, University of Málaga, Campus de Teatinos s/n, Málaga 29071, Spain.
authors.forename: María Moreno
authors.initials: MM
authors.lastname: Oliva
authors.forename: Ted M
authors.initials: TM
authors.lastname: Pappenfus
authors.forename: Jacob H
authors.initials: JH
authors.lastname: Melby
authors.forename: Kathryn M
authors.initials: KM
authors.lastname: Schwaderer
authors.forename: Jared C
authors.initials: JC
authors.lastname: Johnson
authors.forename: Kari A
authors.initials: KA
authors.lastname: McGee
authors.forename: Demetrio A
authors.initials: DA
authors.lastname: da Silva Filho
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Bredas
authors.forename: Juan
authors.initials: J
authors.lastname: Casado
authors.forename: Juan T
authors.initials: JT
authors.lastname: López Navarrete