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Volumn 105, Issue 7, 2001, Pages 1214-1222

Energy transfer to the low-energy triplet states of 1,3-dicarbonylazomethine dyes: The role of unique geometries and nonadiabatic behavior

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON TRANSPORT PROPERTIES; GROUND STATE; HYDROGEN BONDS; ISOMERS; KETONES; RATE CONSTANTS;

EID: 0035249898     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp002793h     Document Type: Article
Times cited : (10)

References (71)
  • 2
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    • James, T. H., Ed. Macmillan Publishing Co.: New York
    • (a) James, T. H., Ed. Theory of the Photographic Process, 4th ed.; Macmillan Publishing Co.: New York, 1978.
    • (1978) Theory of the Photographic Process, 4th Ed.
  • 10
    • 0342613786 scopus 로고    scopus 로고
    • Excited singlet states of pyrazolotriazole azomethine dyes: Are they hot? Theory and experiment
    • San Francisco, CA
    • Kondakov, D. "Excited singlet states of pyrazolotriazole azomethine dyes: are they hot? Theory and experiment." Presented at the 219th ACS National Meeting, 2000, San Francisco, CA.
    • (2000) 219th ACS National Meeting
    • Kondakov, D.1
  • 23
    • 0002447405 scopus 로고
    • Energy Transfer and Photochemistry
    • Leermakers, P. A., Evans, T. R., Eds.; Interscience Publishers: New York
    • Lamola, A. A.; Turro, N. J. Energy Transfer and Photochemistry. In Techniques of Organic Chemistry; Leermakers, P. A., Evans, T. R., Eds.; Interscience Publishers: New York, 1969.
    • (1969) Techniques of Organic Chemistry
    • Lamola, A.A.1    Turro, N.J.2
  • 25
    • 85037306225 scopus 로고    scopus 로고
    • note
    • 0 = κ(kT/h), κ accounts for the possibility that the activated complex (transition state) will give the reactants back, rather than the products. For discussion, see chapter 4 in Laidler, K. J. Chemical Kinetics.
  • 27
    • 85037311539 scopus 로고    scopus 로고
    • note
    • The term "nonadiabatic" is used in this study in a generic sense to denote a reaction having rate constant with a small preexponential value, in a way similar to that adopted by Balzani. For a discussion on the use of the term in reaction kinetics see Laidler in the next reference.
  • 29
    • 85037296031 scopus 로고    scopus 로고
    • The registry numbers of 1 and 2 are 4754-92-1, and 4755-00-4, respectively. 3 is a new compound and was prepared by a similar way as described for 1 and 2 in ref 10
    • The registry numbers of 1 and 2 are 4754-92-1, and 4755-00-4, respectively. 3 is a new compound and was prepared by a similar way as described for 1 and 2 in ref 10.
  • 43
    • 85037313239 scopus 로고    scopus 로고
    • note
    • 2 in data fitting, but does not change the conclusions of the study.
  • 44
    • 85037291031 scopus 로고    scopus 로고
    • Nonlinear regression was done using Mathematica V.3.0.1
    • Nonlinear regression was done using Mathematica V.3.0.1.
  • 54
    • 85037312000 scopus 로고    scopus 로고
    • Cerius v3.0, Molecular Simulation Inc., San Diego, 1997
    • Cerius v3.0, Molecular Simulation Inc., San Diego, 1997.
  • 57
    • 85037292178 scopus 로고    scopus 로고
    • note
    • The chemical shift of the amide proton of 1 appears at 9.42 ppm (CD2C12, 25 °C). The relatively low field value of this proton can be attributed to a presence of a weak side-on intramolecular hydrogen bond between this proton and the azomethine nitrogen.
  • 64
    • 0004204133 scopus 로고
    • Benjamin/ Cummings Publishing Co.: Menlo Park, CA
    • (a) Turro, N. J. Modem Molecular Photochemistry; Benjamin/ Cummings Publishing Co.: Menlo Park, CA, 1978.
    • (1978) Modem Molecular Photochemistry
    • Turro, N.J.1
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    • max
    • max.
  • 70
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    • note
    • 2 at 30 °C appear as sharp peaks at 8.47 and 9.37 ppm in the NMR spectrum. Upon cooling, the peak at 8.47 ppm (peak width = 6.6 Hz) is gradually shifted to lower field values, and is slightly broadened, reflecting presence of two rapidly exchanging species in solution having very different environments around this amide proton. At -70°, the chemical shift of this peak is 9.56 ppm, and the peak width is 18.7 Hz. These environments are consistent with presence or absence of a strong intramolecular H-bond involving this proton. The value of the peak at 9.37 ppm is similar to the chemical shift of the anilide proton of 1 (9.42 ppm), and may therefore be attributed to a proton having a side-on intramolecual H-bond with the azomethine nitogen. The chemical shift of this proton does not change upon cooling. All these results are consistent with the proposition that the two exchanging species differ only in the rotation of one of the anilide groups. We thank Andrew Hoteling for doing the NMR measurements.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.