Cis-Trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations

被引：44
|
作者：
Wazzan, Nuha A. [1 ]
Richardson, Patricia R. [1 ]
Jones, Anita C. [1 ]
机构：
[1] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
来源：
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES | 2010年 / 9卷 / 07期
关键词：
SUBSTITUTED AZOBENZENES; THERMAL-ISOMERIZATION; INVERSION MECHANISM; SOLVENT; DERIVATIVES; PHOTOISOMERIZATION; TEMPERATURE; ABSORPTION; LIGHT;
D O I：
10.1039/c0pp00056f
中图分类号：
Q5 [生物化学]; Q7 [分子生物学];
学科分类号：
071010 ; 081704 ;
摘要：
In a combined experimental and computational study of a group of para-substituted azobenzenes, the effects of substituents and solvent on the kinetics of thermal cis-to-trans isomerisation have been examined and the success of DFT calculations in predicting kinetic parameters assessed. Mono-substituted species are predicted to isomerise by inversion in both non-polar and polar solvent, whereas for push-pull azobenzenes the mechanism is predicted to change from inversion to rotation on going from non-polar to polar solvent. Computed free energies of activation qualitatively reproduce experimental trends but do not quantitatively predict the kinetics of cis-trans isomerisation. The polarisable continuum model of solvation fails to predict the experimentally observed influence of solvent on the entropy of activation.
引用
收藏
页码：968 / 974
页数：7
相关论文
共 50 条
  • [1] Cis-Trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations
    Nuha A. Wazzan
    Patricia R. Richardson
    Anita C. Jones
    Photochemical & Photobiological Sciences, 2010, 9 : 968 - 974
  • [2] Cis-trans isomerism and conformational structure of N-methyldodecanelactam as studied by NMR, IR and Raman spectroscopy and by theoretical calculations
    Doskocilova, D.
    Dybal, J.
    Schmidt, P.
    Schneider, B.
    Journal of Molecular Structure, 350 (01):
  • [3] CIS-TRANS ISOMERISM AND CONFORMATIONAL STRUCTURE OF N-METHYLDODECANELACTAM AS STUDIED BY NMR, IR AND RAMAN-SPECTROSCOPY AND BY THEORETICAL CALCULATIONS
    DOSKOCILOVA, D
    DYBAL, J
    SCHMIDT, P
    SCHNEIDER, B
    KRIZ, J
    JOURNAL OF MOLECULAR STRUCTURE, 1995, 350 (01) : 9 - 18
  • [4] CIS-TRANS ENERGETICS IN UREA AND ACETAMIDE STUDIED BY DEUTERIUM NMR
    WILLIAMS, JC
    MCDERMOTT, AE
    JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (47): : 12393 - 12398
  • [5] PEPTIDYL-PROLYL CIS-TRANS ISOMERASE ACTIVITY AS STUDIED BY DYNAMIC PROTON NMR-SPECTROSCOPY
    HUBNER, D
    DRAKENBERG, T
    FORSEN, S
    FISCHER, G
    FEBS LETTERS, 1991, 284 (01) : 79 - 81
  • [6] Isomerisation of phenanthrene dication studied by tagging photodissociation ion spectroscopy and DFT calculations
    Pereverzev, Aleksandr Y.
    Rossi, Corentin
    Roithova, Jana
    MOLECULAR PHYSICS, 2024, 122 (1-2)
  • [7] Charge transfer excited state studied by fluorescence and its role in cis-trans isomerisation in anthrylethylene derivatives
    Reddy, AM
    Gopal, VR
    Rao, VJ
    RADIATION PHYSICS AND CHEMISTRY, 1997, 49 (01): : 119 - 125
  • [8] Photoisomerization dynamics of trans-trans, cis-trans, and cis-cis diphenylbutadiene from broadband transient absorption spectroscopy and calculations
    Krohn, O. A.
    Quick, M.
    Sudarkova, S. M.
    Ioffe, I. N.
    Richter, C.
    Kovalenko, S. A.
    JOURNAL OF CHEMICAL PHYSICS, 2020, 152 (22): : 224305
  • [9] Solid polymer electrolytes studied by NMR spectroscopy and DFT calculations
    Spevácek, J
    Brus, J
    Dybal, J
    MACROMOLECULAR SYMPOSIA, 2006, 235 : 57 - 63
  • [10] Au nanoparticle scaffolds modulating intermolecular interactions among the conjugated azobenzenes chemisorbed on curved surfaces: tuning the kinetics of cis-trans isomerisation
    Raimondo, Corinna
    Kenens, Bart
    Reinders, Federica
    Mayor, Marcel
    Uji-i, Hiroshi
    Samori, Paolo
    NANOSCALE, 2015, 7 (33) : 13836 - 13839
12345