Trans- and cis-stilbene isolated in cryogenic argon and xenon matrices

ÜNSALAN O., Kuş N., Jarmelo S., Fausto R.

Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, cilt.136, sa.PA, ss.81-94, 2015 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 136 Sayı: PA
  • Basım Tarihi: 2015
  • Doi Numarası: 10.1016/j.saa.2013.10.050
  • Dergi Adı: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.81-94
  • Anahtar Kelimeler: Trans- and cis-stilbene, Matrix isolation IR spectroscopy, DFT(B3LYP)/6-311++G(d,p) calculations, Cis -> trans photoisomerization, GAS ELECTRON-DIFFRACTION, MOLECULAR-STRUCTURE, AB-INITIO, PICOSECOND DYNAMICS, VIBRATIONAL-SPECTRA, CRYSTAL-STRUCTURE, SUPERSONIC BEAMS, PHOTOISOMERIZATION, ENERGY, ISOMERIZATION
  • Anadolu Üniversitesi Adresli: Evet

Özet

© 2013 Elsevier B.V. All rights reserved.Monomers of trans- (TS) and cis-stilbene (CS) were isolated in cryogenic argon and xenon matrices, and their infrared (IR) spectra were fully assigned and interpreted. The interpretation of the vibrational spectra received support from theoretical calculations undertaken at the DFT(B3LYP)/6-311++G(d,p) level of theory. In situ broadband UV irradiation of the matrix-isolated CS led to its isomerization to TS, which appeared in the photolysed matrices in both non-planar and planar configurations. The non-planar species was found to convert into the more stable planar form upon subsequent annealing of the matrices at higher temperature. TS was found to be photostable under the used experimental conditions. The structure of the non-planar TS form was assigned based on the comparison of its observed IR spectrum with those theoretically predicted for different conformations of TS. Chemometrics was used to make this assignment. Additional reasoning on the structure of the studied stilbenes is presented taking as basis results of the Natural Bond Orbital analysis.