Electron affinities of aza-substituted polycyclic aromatic hydrocarbons

1989 ◽  
Vol 67 (10) ◽  
pp. 1628-1631 ◽  
Author(s):  
Glen W. Dillow ◽  
P. Kebarle
Keyword(s):  
Electron Transfer ◽  
Gas Phase ◽  
Aromatic Hydrocarbons ◽  
Radical Anions ◽  
Electron Affinities ◽  
Reduction Potentials ◽  
Dilute Gas ◽  
Solvation Energies ◽  
Polycyclic Aromatic ◽  
Electron Reduction

Electron affinities for aza-substituted polycyclic aromatics were determined from measurements of electron transfer equilibria in the dilute gas phase with a pulsed electron high pressure mass spectrometer (PHPMS). These are (in kcal/mol): quinazoline (12.7), quinoxaline (15.8), cinnoline (16.0), acridine (20.3), benzo[c]cinnoline (20.6), pyrido[2,3-b]pyrazine (22.5), phenazine (29.5). Solvation energies of the corresponding radical anions in acetonitrile and dimethylformamide are derived from the gas phase data and literature on electron reduction potentials in solution. An observed linear relationship between the electron affinities and the reduction potentials allows estimates of electron affinities to be made for 12 aza compounds whose EA's are too low to be measured with the present method. Keywords: aza-substituted aromatic hydrocarbons, electron affinities, electron transfer, radical anions, reduction potentials, solvation energies of radical anions, stabilities of radical anions.

Gas phase adiabatic electron affinities of cyclopenta-fused polycyclic aromatic hydrocarbons

2008 ◽  
Vol 454 (1-3) ◽  
pp. 30-35 ◽  
Author(s):  
Petar D. Todorov ◽  
Carola Koper ◽  
Joop H. van Lenthe ◽  
Leonardus W. Jenneskens
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Gas Phase ◽  
Aromatic Hydrocarbons ◽  
Electron Affinities ◽  
Polycyclic Aromatic

Chemistry of radical ions: the absolute rate constant of dimerization of radical anions of 1 ,1-diphenyl ethylene

1965 ◽  
Vol 288 (1413) ◽  
pp. 212-223 ◽  
Keyword(s):  
Electron Transfer ◽  
Rate Constant ◽  
Transfer Process ◽  
Aromatic Hydrocarbons ◽  
Radical Anions ◽  
Electron Affinities ◽  
Absolute Rate ◽  
Radical Ions ◽  
Electron Transfer Process ◽  
Absolute Rate Constant

The combination of the labile radical ions, (Ph 2 C:CH 2 )7~, Na+, into dimeric dianions Na + , C - (Ph) 2 .CH 2 .CH 2 .C(Ph) - 2, Na+ was investigated by a flow and a stopflow technique. The bimolecular rate constant of combination was found to be 2 to 3 x 106 1. mole-1 s-1. The reaction was initiated by an electron transfer naphthalene^ + (P/*,2C:CH2) naphthalene+ (P/*,2C:CH^) or terphenylener + (P7fc2C:CH2) ⇔ terphenylene + (Pfe2C:CH^). The equilibrium constant of the first electron transfer process was found to be 20 and of the second about 16. These results are consistent with recent determinations of electron affinities of aromatic hydrocarbons.

Electron affinities of substituted nitrobenzenes

1989 ◽  
Vol 67 (4) ◽  
pp. 603-610 ◽  
Author(s):  
S. Chowdhury ◽  
H. Kishi ◽  
G. W. Dillow ◽  
P. Kebarle
Keyword(s):  
High Pressure ◽  
Electron Transfer ◽  
Gas Phase ◽  
Substituent Effects ◽  
Negative Ions ◽  
Radical Anions ◽  
Electron Affinities ◽  
Frontier Orbital ◽  
Data Set ◽  
Qualitative Discussion

The electron affinities of 14 substituted nitrobenzenes including nitrobiphenyls were determined by measurement of electron transfer equilibria [1] in the gas phase with a pulsed high pressure mass spectrometer: A− + B = A + B− [1]. These data, when combined with previous determinations from this laboratory, lead to electron affinities for 35 substituted nitrobenzenes and provide a comprehensive data set for the examination of substituent effects. The data are used to derive Taft gas-phase substituent parameters. A qualitative discussion based on frontier orbital molecular theory examines the substituent effect on the benzene and nitrobenzene LUMOs. The lifetimes for electron autodetachment from excited nitrobenzene negative ions, (A−)*, studied earlier by Christophorou, are examined in light of the present electron affinity data. Keywords: electron affinities, substituent effects, frontier orbital treatment, electron autodetachment from nitrobenzene radical anions.

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