Exploration of the electronic structure of dendrimerlike acetylene-bridged oligothiophenes by correlating Raman spectroscopy, electrochemistry, and theory.
A series of radial thiophene-based structures consisting of a central benzene or thiophene ring surrounded by acetylene-bridged terthienyl arms has been investigated by physical and theoretical methods. Fourier transform Raman spectroscopy of the neutral solids shows that the terthiophene arms are weakly coupled across the core (benzene plus acetylene groups) likely due to cross-conjugation or meta-conjugation effects that may prevent full delocalization. By increasing the number of arms around the central ring, the electronic structure of the molecules seems to be affected only at the core, whereas the outer terthiophene arms remain almost unaltered. Raman spectroelectrochemistry and quantum chemical calculations provide further insight into the charge delocalization of the oxidized species. There is no evidence to suggest that these oxidized forms, obtained upon electrochemical doping of the molecules, show charge delocalization across the core.
Casado
Juan
J
Department of Physical Chemistry, University of Málaga, Campus de Teatìnos s/n, Málaga 29071, Spain. casado@uma.es
Pappenfus
Ted M
TM
Mann
Kent R
KR
Hernández
Victor
V
López Navarrete
Juan T
JT
D000114:Acetylene / Q000737:chemistry*; D050091:Dendrimers / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods; D004581:Electronics; D011108:Polymers / Q000737:chemistry*; D013059:Spectrum Analysis, Raman / Q000379:methods; D013876:Thiophenes / Q000737:chemistry*
D050091:Dendrimers; D011108:Polymers; D013876:Thiophenes; C066730:polythiophene; D000114:Acetylene