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Volumn 128, Issue 51, 2006, Pages 16446-16447

Ultrafast spectroscopic study of the photochemistry and photophysics of arylhalodiazirines: Direct observation of carbene and zwitterion formation

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; AMPHOLYTE; AZIRINE DERIVATIVE; CARBENE; CYCLOHEXANE; FLUOROPHENYLDIAZIRINE; HALIDE; SOLVENT; UNCLASSIFIED DRUG;

EID: 33845962306     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja067205d     Document Type: Article
Times cited : (23)

References (18)
  • 5
    • 33845917796 scopus 로고    scopus 로고
    • Details of the Rutgers spectrometer are given in the Supporting Information
    • Details of the Rutgers spectrometer are given in the Supporting Information.
  • 6
    • 0001524770 scopus 로고    scopus 로고
    • Gould, I. R.; Turro, N. J.; Butcher, J., Jr.; Doubleday, C., Jr.; Hacker, N. P.; Lehr, G. F.; Moss, R. A.; Cox, D. P.; Guo, W.; Munjal, R. C.; Perez, L. A.; Fedorynski, M. Tetrahedron 1985, 41, 1587.
    • Gould, I. R.; Turro, N. J.; Butcher, J., Jr.; Doubleday, C., Jr.; Hacker, N. P.; Lehr, G. F.; Moss, R. A.; Cox, D. P.; Guo, W.; Munjal, R. C.; Perez, L. A.; Fedorynski, M. Tetrahedron 1985, 41, 1587.
  • 7
    • 33845923406 scopus 로고    scopus 로고
    • 8
    • 8
  • 12
    • 33845941959 scopus 로고    scopus 로고
    • In acetonitrile, the ratio of fast/slow transient decay increases from fluoro-to chloro- to bromophenyldiazirine, hence the decay of the fluoro compound alone appears to be substantially monoexponential. The shape of the transient spectra obtained by excitation of the arylhalodiazirines does not change with time, consistent with the presence of a single absorbing intermediate in each system. Control experiments with all three halophenyldiazirine.s reveal that ultrafast photolysis (270 nm) of acetonitrile solutions of arylhalodiazirines, previously bleached by exposure to 266 nm radiation, does not produce the same transients observed by photolysis of fresh solutions of the diazirines. This demonstrates that the initially observed transients for the studied diazirines are not formed by re-excitation of stable reaction products
    • In acetonitrile, the ratio of fast/slow transient decay increases from fluoro-to chloro- to bromophenyldiazirine, hence the decay of the fluoro compound alone appears to be substantially monoexponential. The shape of the transient spectra obtained by excitation of the arylhalodiazirines does not change with time, consistent with the presence of a single absorbing intermediate in each system. Control experiments with all three halophenyldiazirine.s reveal that ultrafast photolysis (270 nm) of acetonitrile solutions of arylhalodiazirines, previously bleached by exposure to 266 nm radiation, does not produce the same transients observed by photolysis of fresh solutions of the diazirines. This demonstrates that the initially observed transients for the studied diazirines are not formed by re-excitation of stable reaction products.
  • 13
    • 33845917041 scopus 로고    scopus 로고
    • The picosecond growth of transient absorption is only observed with bromophenylcarbene because it has the longest wavelength absorption Figure S9, 6 and we are now monitoring the center of the band
    • 6 and we are now monitoring the center of the band.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.