Ab initio computation of electron affinities of substituted benzalacetophenones (chalcones): a new approach to substituent effects in organic electrochemistry

• Published in: Electrochimica acta Vol. 50; no. 4; pp. 1039 - 1047
• Main Authors: Hicks, Latorya D., Fry, Albert J., Kurzweil, Vanessa C.
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 15.12.2004; Elsevier
• Subjects: Ab initio computations; Atomic and molecular physics; Benzalacetophenones; Chalcones; Density functional theory; Exact sciences and technology; Ionization potentials, electron affinities, molecular core binding energy; Molecular properties and interactions with photons; Physics; Properties of molecules and molecular ions; Substituent effects; Substituent effects; Density functional theory; Ab initio computations; Chalcones; Benzalacetophenones; Substituent effect; Hartree-Fock calculations; Electronic properties; Electron affinity; Theoretical study; Voltammetry; Reduction potential; Experimental study; Density functional method; Benzenic compound; Ab initio calculations; NMR spectroscopy; Organic compounds
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2004.08.003

The electron affinities (EAs) of a training set of 29 monosubstituted benzalacetophenones (chalcones) were computed at the ab initio density functional B3LYP/6-31G * level of theory. The EAs and experimental reduction potentials of the training set are highly linearly correlated (correlation coefficient of 0.969 and standard deviation of 10.8 mV). An additional 72 di-, tri-, and tetrasubstituted chalcones were then synthesized. Their reduction potentials were predicted from computed EAs using the linear correlation derived from the training set. Agreement between the experimental and computed reduction potentials is remarkably good, with a standard deviation of less than 22 mV for this very large set of substances whose potentials extend over a range of almost 700 mV.