An improved correlation between polarographic reduction potential and huckel lumo energy. Application to non-benzenoid hydrocarbons

Fry, Albert J.; Fox, Peter C.

doi:10.1016/s0040-4020(01)82074-3

Cited by 17 publications

(9 citation statements)

References 37 publications

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“…Here we show that CP-PAH with peripheral pentagons are readily reduced and, consequently, will possess high electron affinities. In contrast to previous reports, in which the redox properties of (other) non-alternant PAH were studied, 25,26 a good linear correlation is found between the first reduction potentials [E 1/2 (0/À1) V vs. SCE] and their standard Hu ¨ckel Àe LUMO (b) energies that encompasses the whole series of alternant PAH, and, corresponding non-alternant mono-and bis-CP-PAH (1-23) of Scheme 1. It is shown that upon reduction of CP-PAH with peripheral pentagons the additional electrons will occupy the cyclopenta-moieties furnishing 6p-electron cyclopentadienide sub-structures.…”

Section: Introductioncontrasting

confidence: 60%

“…( 1 x The linear correlations could be further improved by adjusting the exchange integrals (b) making use of p-bond orders (p). 26 Hu ¨ckel theory apparently captures both qualitatively and (semi-)quantitatively their first reduction process.…”

Section: (Ii) Hu ¨Ckel Analysismentioning

confidence: 96%

“…31 However for non-alternant PAH containing odd-membered rings as a part of their polycyclic p-conjugated skeleton similar linear correlations were not found. 25,26 This is commonly attributed to the fact that at the Hu ¨ckel level of theory, non-alternant PAH possess p molecular orbitals that are positioned asymmetrically around the a-level and p atomic charge densities that deviate from unity. Hence, the assumption of equal a in standard Hu ¨ckel theory is then untenable.…”

Section: (Ii) Hu ¨Ckel Analysismentioning

confidence: 99%

See 2 more Smart Citations

Redox properties of non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons: The effect of peripheral pentagon annelation

Koper

Sarobe

Jenneskens

2004

Phys. Chem. Chem. Phys.

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Section: Introductioncontrasting

confidence: 60%

Section: (Ii) Hu ¨Ckel Analysismentioning

confidence: 96%

Section: (Ii) Hu ¨Ckel Analysismentioning

confidence: 99%

See 1 more Smart Citation

Redox properties of non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons: The effect of peripheral pentagon annelation

Koper

Sarobe

Jenneskens

2004

Phys. Chem. Chem. Phys.

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“…As an alternative to the Born-Haber cycle methods, linear relationships between molecular orbital energies and the ability of a molecule to accept or donate an electron are among the earliest relationships [25,26] that were considered in the literature and have been used extensively for specific families [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] of molecules. The use of a linear correlation of calculated frontier orbital energies (highest occupied molecular orbital (HOMO) energy for oxidation, lowest unoccupied molecular orbital (LUMO) energy for reduction) of the singlet ground state molecules with their experimentally measured redox potentials is an even simpler way to estimate the redox potentials of unknown molecules.…”

Section: Introductionmentioning

confidence: 99%

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

Méndez-Hernández

Gillmore

Montano

et al. 2015

J of Physical Organic Chem

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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. Copyright © 2015 John Wiley & Sons, Ltd.

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“…A suite of computational programs was used to analyze the orbital energies and geometries of the molecules under investigation. Orbital energies were calculated using two Hückel MO programs, OMEGAMO 9 and Extended Hückel, 18 by PM3 19 …”

Section: Generalmentioning

confidence: 99%

Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution

Steffen

Plummer

Braley

et al. 1997

J. Phys. Org. Chem.

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The oxidation and reduction potentials of a series of related even non-alternant derivatives of 7,14-disubstituted acenaphth[1,2-k] fluoranthenes, and also fluoranthene, 7,10-diphenylfluoranthene and 8,9-dihydrodiindeno[1,2-j;2Ј,1Ј-] fluoranthene, were determined in organic solvents by cyclic voltammetry. The effects of steric hindrance on conjugation of the substituents with the central polycyclic aromatic hydrocarbon nucleus were evaluated. The semi-empirical molecular orbital calculation programs OMEGAMO, Extended Hückel, AM1 and PM3 were used to obtain optimal geometries and calculated HOMO and LUMO energies. As a further refinement, COSMO solvation was included in the AM1 calculations. The redox properties were correlated with data derived from the various semi-empirical calculations and the quality of these correlations is discussed. Inclusion of solvation energies in the computed molecular orbital energies results in a significant improvement in the correlation between observed and calculated oxidation potentials.

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An improved correlation between polarographic reduction potential and huckel lumo energy. Application to non-benzenoid hydrocarbons

Cited by 17 publications

References 37 publications

Redox properties of non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons: The effect of peripheral pentagon annelation

Redox properties of non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons: The effect of peripheral pentagon annelation

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

Electron transfer properties of non-alternant, substituted compounds related to fluoranthene. Experimental determination and theoretical modeling of electrochemical oxidation and reduction potentials in non-aqueous solution

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