El Instituto Politécnico Nacional
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http://repositoriodigital.ipn.mx/handle/123456789/10637| Título : | Tuning Aryl, Hydrazine Radical Cation Electronic Interactions Using Substitutent Effects |
| Palabras clave : | Resonance Raman Absorption |
| Fecha de publicación : | 16-ene-2013 |
| Editorial : | Journal of Physical Chemistry A |
| Descripción : | Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)•+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X)•+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)•+ and 1- and 2(OMe)•+. The calculated geometries and optical absorption spectra for 2(Cl)•+ demonstrate that p-C6H4Cl lies between p-C6H4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)•+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λv sym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X ) H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ( 600 cm-1, which does not vary regularly with electron donating power of the X substituent. |
| URI : | http://www.repositoriodigital.ipn.mx/handle/123456789/10637 |
| Otros identificadores : | 1089-5639 http://hdl.handle.net/123456789/116 |
| Aparece en las colecciones: | Doctorado |
Ficheros en este ítem:
| Fichero | Descripción | Tamaño | Formato | |
|---|---|---|---|---|
| JPC A_p_Cl 2008.pdf | 862.14 kB | Adobe PDF | Visualizar/Abrir |
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