Investigation of structure-spectroscopy-function relationship of two-dimensional J-aggregates of tetrachlorobenzimidazolocarbocyanine preferentially oriented in poly-vinyl-alcohol thin films

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Gulen D., Atasoylu O., ÖZÇELİK S.

CHEMICAL PHYSICS, cilt.355, sa.1, ss.73-80, 2009 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 355 Sayı: 1
  • Basım Tarihi: 2009
  • Doi Numarası: 10.1016/j.chemphys.2008.11.005
  • Dergi Adı: CHEMICAL PHYSICS
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.73-80
  • Anahtar Kelimeler: J-aggregates, Frenkel exciton, Phonon-assisted exciton relaxation, Davydov splitting, Polarized UV-Vis absorption, Vertical spin coating, Cyanines, CARBOCYANINE DYE, FLUORESCENCE, FABRICATION, ASSEMBLIES, DYNAMICS, EXCITONS, ENERGY, MODEL
  • Orta Doğu Teknik Üniversitesi Adresli: Evet

Özet

The structure-spectroscopy-function relationship of 1,1',1,3,3'-tetraethyl-5,5',6,6'-tetrachlorobenzimidazolocarbocyanine (TTBC) aggregates is studied using a combination of experimental and theoretical techniques. The aggregates are macroscopically aligned in poly-vinyl-alcohol thin films by vertical spin coating. Angular dependence of the UV-Vis spectra is measured at eleven different orientations between the electric field polarization and the macroscopic alignment axis. The aggregates are characterized by a pair of Davydov split bands with opposite polarization behaviors: an H-band (505 nm) and a J-band (594 nm) polarized respectively, close to being parallel and perpendicular to the alignment axis. Spectral response is interpreted via simulations within the Frenkel exciton formalism. TTBC aggregates are shown to assume very similar internal molecular packing (herringbone) and dynamics of excited states (phonon-assisted intraband and interband relaxations) in ionic aqueous solution and in thin films. The general conclusions on the structure-spectroscopy-function relationship are expected to hold for other cyanine aggregates with the same generic spectral features. (C) 2008 Elsevier B.V. All rights reserved.