Building and testing correlations for the estimation of one-electron reduction potentials of a diverse set of organic molecules

Dalvin D. Méndez-Hernández, Jason G. Gillmore, Luis A. Montano, John Devens Gust, Thomas A Moore, Ana L Moore, Vladimiro Mujica

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

We describe and evaluate a method for computationally predicting reduction potentials of a diverse group of organic molecules by linearly correlating calculated lowest unoccupied molecular orbital energies with ground state reduction potentials measured in acetonitrile. The approach is shown to provide a unique combination of extreme computational simplicity and excellent accuracy across a diverse range of organic structures and a wide window of reduction potentials. A disparate set of molecules (74 compounds belonging to six distinct structural families, comprised of molecules containing C, H, N, O, F, Cl, and Br, with functional groups including esters, ketones, halides, nitriles, quinones, alkenes, arenes, heteroarenes, and pyridinium and higher benzologs, all containing conjugated pi systems, spanning a 3.5-V range of reduction potentials) was used to build the correlations. This methodology was found to be computationally inexpensive compared with other approaches and to permit the useful prediction of reduction potentials of additional molecules of diverse structural types not included in the families used to determine the correlation parameters. The effects of varying the basis set used in the B3LYP electronic structure calculations and including solvent (compared with calculations in gas phase) were also examined. It was found that the inclusion of a continuum solvent model in the calculations was required for accurate results, particularly when including cationic species in the correlations (although when only neutral molecules were examined, reasonable results could even be obtained in vacuo). Several of the best correlations were used to predict the reduction potentials of seven much larger and structurally diverse chromophores that were not included in the correlation data set. Strong correlations (r2 values > 0.99) with very good predictive abilities (root mean square deviation <60 mV) were found. This extremely simple and computationally efficient entirely closed-shell methodology is proven robust and useful for the design of new molecules capable of participating in redox processes, including electron transfer reactions.

Original languageEnglish
Pages (from-to)320-328
Number of pages9
JournalJournal of Physical Organic Chemistry
Volume28
Issue number5
DOIs
Publication statusPublished - May 1 2015

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Molecules
Electrons
Testing
molecules
electrons
Quinones
Nitriles
methodology
data correlation
Alkenes
Molecular orbitals
Chromophores
Ketones
nitriles
Ground state
quinones
Functional groups
Electronic structure
ketones
Esters

Keywords

  • computational electrochemistry
  • frontier orbitals
  • linear correlation
  • LUMO energy
  • redox potentials

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Building and testing correlations for the estimation of one-electron reduction potentials of a diverse set of organic molecules. / Méndez-Hernández, Dalvin D.; Gillmore, Jason G.; Montano, Luis A.; Gust, John Devens; Moore, Thomas A; Moore, Ana L; Mujica, Vladimiro.

In: Journal of Physical Organic Chemistry, Vol. 28, No. 5, 01.05.2015, p. 320-328.

Research output: Contribution to journalArticle

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