A Correlation of Electrochemical Oxidation Potential of Organic Compounds with Photoionization Potential

Neikam, W. C.; Dimeler, G. R.; Desmond, M. M.

doi:10.1149/1.2425951

Cited by 68 publications

(30 citation statements)

References 5 publications

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“…However, in this case, the olefins 9 and 10 were not the major products. Instead, a colourless crystalline solid was isolated which was characterized as having the structure 1-(2,4-dicyanopheny1)-2,3-dimethyl-2-butene (14). Only this isomer was formed; no trace of 15 was detected (Fig.…”

Section: Resultsmentioning

confidence: 99%

Radical ions in photochemistry. 15. The photosubstitution reaction between dicyanobenzenes and alkyl olefins

Borg¹,

Arnold²,

Cameron³

1984

Can. J. Chem.

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Can. J. Chem. 62, (785 (1984). ' The photosubstitution (electron transfer) reaction between 1,4-dicyanobenzene (1) and 2,3-dimethyl-2-butene (2), which gives I-(4-cyanophenyl)-2,3-dimethyl-2-butene (3) and 3-(4-cyanopheny1)-2,3-dimcthyl-I-butene (4). has been extended to other dicyanobenzene-olefin mixtures. Substitution of a cyano group occurs when both 1 or 1,2-dicyanobenzene (5) are irradiated in acetonitrile solution, in the presence of 2 or cyclohexcne (16). Under comparable conditions, 1.3-dicyanobenzene (6) failed to react. Little or no substitut~on was observed in any case when the olefin was methylpropene (19). ' The results for 1 and 5 are in agreement with empirical free energy calculations (Weller equation) for the electron transfer process which, however, fail to explain the general lack of reactivity of 1,3-dicyanobenzene. Phenanthrene (11) has been shown to photosensitize the photosubstitution reaction between dicyanobenzenes and 2. Under these conditions the olefin reacts with 6 predominantly at the 4-position, resulting in overall substitution of a hydrogen atom. This reaction occurs regiospecifically, resulting in the formation of only one of the two possible isomeric side chains. The mechanistic details of these reactions have been substantiated by means of deuterium labelling studies. The aromatic nitriles also undergo photosubstitution by 2, in acetonitrile-methanol solution, resulting in methanol-incorporated products. Whereas reaction with 1 or 5 results in substitution of a cyano group, 6 was observed to give isomeric dicyanocyclohexenes, resulting from initial reaction at the 4-position, followed by reduction. A detailed mechanism for this secondary photoreduction has been substantiated by deuterium labelling studies. The anomalous behaviour of 1,3-dicyanobenzene has been attributed to a difference in the react~vity of the radical anion. marquages par le deutCrium permettent de confirmer les dttails mkcanistiques dc ces rCactions. Les nitriles aromatiques, en solution dans des milanges d'acktonitrile et de methanol, subissent aussi des photosubstitutions par 2; il y a formation de produits ayant incorporC du mCthanol. Alors que la rCaction des composCs 1 ou 5 conduit a la substitution d'un groupe cyano, on a observC que le compost 6 donne des dicyanocyclohextnes isomkres qui resultent d'une rkaction initiale en position 4, suivie d'une riduction. Des Ctudes impliquant des marquages par du deuterium ont permis de confirmer le mCcanisme dCtaillC de cette photorCduction secondaire. On attribue Ie comportement anormal du dicyano-I ,3 benzkne a la diffkrence de rCactivitC de I'anion radical.[Traduit par le journal]

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Section: Resultsmentioning

confidence: 99%

Radical ions in photochemistry. 15. The photosubstitution reaction between dicyanobenzenes and alkyl olefins

Borg¹,

Arnold²,

Cameron³

1984

Can. J. Chem.

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“…First, as already mentioned, the Fc + /Fc formal potential may exhibit environmental effects and, as a result, the comparison of potentials obtained in different solvents or with different supporting electrolytes cannot be done with high levels of accuracy. Second, in solvents of intermediate or low polarity, such as the widely used dichloromethane (CH 2 Cl 2 ), the measurement of the Fc + /Fc potential against aqueous reference electrodes (Ag/AgCl or SCE, silver/silver chloride or Saturated Calomel Electrode, respectively) is influenced by practical considerations, such as the development of unknown liquid junction potentials between the aqueous filling solution of the reference electrode and the test non‐aqueous solution,16 the clogging of this junction, or the contamination of the test solution by water or ions from the reference electrode filling solution.…”

Section: Electrochemical Methodology To Assess Homo/lumo Energiesmentioning

confidence: 99%

“…These examples show that the formal potential of ferrocene closely match the Connelly and Geiger value of 0.40 V vs. SCE in MeCN. There are other examples where the formal potential of ferrocene is assumed to be 0.40 V versus NHE (or 0.16 V vs. SCE) in 0.1 M Bu 4 N + PF 6 − /MeCN,1–22, 23 while other reports assume this value to be 0.20 V versus NHE in 0.1 M Bu 4 N + PF 6 − /MeCN (or –0.04 V vs. SCE) 24–27. Either of these two formal potentials may have originated from early reports,28, 29 but relatively recent experimental work has been done giving different values 19…”

Section: Electrochemical Methodology To Assess Homo/lumo Energiesmentioning

confidence: 99%

Electrochemical Considerations for Determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications

et al. 2011

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Narrow bandgap conjugated polymers in combination with fullerene acceptors are under intense investigation in the field of organic photovoltaics (OPVs). The open circuit voltage, and thereby the power conversion efficiency, of the devices is related to the offset of the frontier orbital energy levels of the donor and acceptor components, which are widely determined by cyclic voltammetry. Inconsistencies have appeared in the use of the ferrocenium/ferrocene (Fc + /Fc) redox couple, as well as the values used for the absolute potentials of standard electrodes, which can complicate the comparison of materials properties and determination of structure/property relationships.

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“…The voltammograms of 10, 3, and 24 are typical examples of electro- chemically reversible, quasireversible, and irreversible systems, respectively. For the reversible systems, midpoint potential between the anodic (E pa ) and cathodic peaks (E pc ), formal potential (E 0 ', is known to exhibit a linear dependence on the ionization potential [33] . On the other hand, for the quasireversible and irreversible systems, E pc and therefore E 0 ' is difficult to determine; so that in this study E pa was employed instead of E 0 '.…”

Section: Resultsmentioning

confidence: 99%

Role of Electron-Donative Dopant Molecules in the Triboelectrification of Polystyrene Films

Hoshino¹,

Oh-oka

Kokado

et al. 2001

Macromol. Chem. Phys.

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The triboelectrification between iron carrier beads and polystyrene films molecularly‐doped with 50 electron‐donative organics are investigated in a nitrogen atmosphere and low humidity (<10% RH) conditions. The electrochemical oxidation potential of the dopants correlates well with the tribocharging amount within the framework of a homologous series of dopant molecules, but turns out not to be a widely applicable and reliable indication. Considerations of liquid‐phase electrochemical oxidations and solid‐phase frictional electrifications lead us to use calculated oxidation potentials instead of the measured one, and it is revealed that a relatively good relation holds between the calculated potential and the charging amount. However, there still exists some dispersion of the data in the relationship. X‐ray photoelectron spectroscopic measurements of the film surfaces, combined with the above findings, reveal that the dopants form charge transfer complexes with environmental dioxygen and that they serve as the positive‐charging sites. This is evidenced by an even more reliable relationship between the charging amount and the binding energy of O1s electrons. A possible mechanism is proposed for the positive charging of organic compounds on the basis of the charge‐transfer model.

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A Correlation of Electrochemical Oxidation Potential of Organic Compounds with Photoionization Potential

Cited by 68 publications

References 5 publications

Radical ions in photochemistry. 15. The photosubstitution reaction between dicyanobenzenes and alkyl olefins

Radical ions in photochemistry. 15. The photosubstitution reaction between dicyanobenzenes and alkyl olefins

Electrochemical Considerations for Determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications

Role of Electron-Donative Dopant Molecules in the Triboelectrification of Polystyrene Films

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