Excited state amino inversion potentials in aniline derivatives: Fluoroanilines and aminopyridines

Gordon, Robert D.; Clark, David R.; Crawley, John; Mitchell, R.W.

doi:10.1016/0584-8539(84)80120-8

Cited by 36 publications

(27 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The origin of the very large red-shift in the S 1 ←S 0 transition energy instead appears to be associated with the difference between the aniline and parafluoroaniline chromophores, themselves. While the electronic origin of DFDPA is found to be red-shifted 1635 cm Ϫ1 from that of para-fluoroaniline, 29 the electronic origin of DPA is similarly found 1571 cm Ϫ1 from that of aniline. 5 The near identity of these values suggests that the extent of conjugation and hence the structure of these two molecules are quite similar and that the nature of the electronic transition is also unaffected by the symmetric para-difluoro substitution.…”

Section: Fluorine Substitutionmentioning

confidence: 82%

Electronic spectroscopy and molecular structure of jet-cooled diphenylamine and diphenylamine derivatives

Tretiakov

Cable

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inLaser induced fluorescence and resonant two-photon ionization spectroscopy of jet-cooled 1-hydroxy-9,10anthraquinone J. Chem. Phys. 122, 034304 (2005); 10.1063/1.1829977 H atom transfer along an ammonia chain: Tunneling and mode selectivity in 7-hydroxyquinoline ( NH 3 ) 3Resonance enhanced multiphoton ionization spectroscopy of jet cooled 12 C 32 S 2 and 12 C 34 S 32 S from 45 500 to 48000 cm−1 Vibrationally resolved electronic spectra of diphenylamine, three deuterated isotopomers, and both para-methyl and para-fluoro substituted derivatives have been recorded in a supersonic jet expansion using resonantly enhanced two-photon ionization. Analysis of these spectra, supported by ab initio calculations, has been used to determine the gas phase structure of diphenylamine. In both the ground and first excited singlet states, an effective C 2 symmetry structure is found in which the nitrogen atom is in a planar configuration and the phenyl rings adopt equal torsional angles. Calculations suggest that large-amplitude motion along the nitrogen inversion coordinate is possible in the ground electronic state. Isotopic substitutions have been used to assign the two low-frequency Franck-Condon active modes to different admixtures of symmetric phenyl torsion and bending about the central nitrogen. Electronic excitation to the S 1 state results in a decrease in the phenyl torsional angles of 7.4°and an increase in the C-N-C bond angle of 4.0°. While spectra of both the para mono-and dimethyl derivatives as well as the para-diflouro derivative indicate that little change occurs in either the physical or electronic structure of the basic chromophore, the spectrum of the monosubstituted para-fluoro derivative is indicative of a substantial perturbation to both.

show abstract

Section: Fluorine Substitutionmentioning

confidence: 82%

Electronic spectroscopy and molecular structure of jet-cooled diphenylamine and diphenylamine derivatives

Tretiakov

Cable

1997

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…For example, haloanilines are widely used as chemical intermediates in the manufacture of drugs, dyes, and pesticides. Many mono-substituted anilines have been studied extensively by various spectroscopic methods [1][2][3][4][5][6]. Di-substituted anilines also play an important role in metabolomics.…”

Section: Introductionmentioning

confidence: 99%

Cation spectroscopy of 3,4-difluoroaniline by two-color resonant two-photon mass-analyzed threshold ionization

Huang

Tzeng

2011

Journal of Molecular Spectroscopy

View full text Add to dashboard Cite

“…In aniline, this mode is prominent in the excitation and emission spectra. [5][6][7][8] As in aniline, an inversion barrier exists at the planar position in the S 0 state. Microwave studies of DMA ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

A re-examination of the S→S1 excitation spectrum of dimethylaniline

Weersink

Wallace

Gordon

1995

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

A new assignment for the S 0 →S 1 transition of N,N-dimethylaniline ͑DMA͒ and related derivatives is presented. The low frequency bands and long Franck-Condon envelope observed in DMA-h 6 and DMA-d 6 are assigned to the coupled methyl torsion mode of the amino group, not to torsion of the amino substituent about the C-N bond. This new assignment is consistent with the change in frequency of the excitation bands upon deuteration of the methyl groups and the strong origin transitions observed in the excitation spectra of other alkyl anilines. The assignment was confirmed by simulations of the excitation spectra of DMA-h 6 and DMA-d 6 , with parameters of the calculated potential energy surface determined to be V 3 ϭ148.0Ϯ0.5 cm Ϫ1 , V ϩ ϭϪ31.6Ϯ0.5 cm Ϫ1 , V Ϫ ϭ8.5Ϯ0.5 cm Ϫ1 , and V 6 ϭϪ15Ϯ0.5 cm Ϫ1 . By Franck-Condon analysis, it was determined that the weak origin transition is due to the shifting of the S 1 torsion minimum by 40°along the gearing coordinate relative to the corresponding minimum in the ground state.

show abstract

Excited state amino inversion potentials in aniline derivatives: Fluoroanilines and aminopyridines

Cited by 36 publications

References 27 publications

Electronic spectroscopy and molecular structure of jet-cooled diphenylamine and diphenylamine derivatives

Electronic spectroscopy and molecular structure of jet-cooled diphenylamine and diphenylamine derivatives

Cation spectroscopy of 3,4-difluoroaniline by two-color resonant two-photon mass-analyzed threshold ionization

A re-examination of the S→S1 excitation spectrum of dimethylaniline

Contact Info

Product

Resources

About