The 6,6-Dicyanopentafulvene Core: A Template for the Design of Electron-Acceptor Compounds
2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, no 22, 8168-8176 p.Article in journal (Refereed) Published
The electron-accepting ability of 6,6-dicyanopentafulvenes (DCFs) can be varied extensively through substitution on the five-membered ring. The reduction potentials for a set of 2,3,4,5-tetraphenyl-substituted DCFs, with varying substituents at the para-position of the phenyl rings, strongly correlate with their Hammett sigma(p)-parameters. By combining cyclic voltammetry with DFT calculations ((U)B3LYP/6-311+G(d)), using the conductor-like polarizable continuum model (CPCM) for implicit solvation, the absolute reduction potentials of a set of twenty DCFs were reproduced with a mean absolute deviation of 0.10eV and a maximum deviation of 0.19eV. Our experimentally investigated DCFs have reduction potentials within 3.67-4.41eV, however, the computations reveal that DCFs with experimental reduction potentials as high as 5.3eV could be achieved, higher than that of F-4-TCNQ (5.02eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6eV.
Place, publisher, year, edition, pages
2015. Vol. 21, no 22, 8168-8176 p.
computational chemistry, density functional calculations, electron acceptors, molecular materials, reduction potentials
IdentifiersURN: urn:nbn:se:uu:diva-256225DOI: 10.1002/chem.201500379ISI: 000354651300027PubMedID: 25917111OAI: oai:DiVA.org:uu-256225DiVA: diva2:826435