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A Theoretical Study of the UV/Visible Absorption and Emission Solvatochromic Properties of Solvent‐Sensitive Dyes
Author(s) -
Han WenGe,
Liu Tiqing,
Himo Fahmi,
Toutchkine Alexei,
Bashford Donald,
Hahn Klaus M.,
Noodleman Louis
Publication year - 2003
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200300801
Subject(s) - solvatochromism , merocyanine , cyanine , nile red , photochemistry , chemistry , bathochromic shift , solvent , solvation , intermolecular force , molecule , solvent effects , absorption (acoustics) , fluorescence , dipole , density functional theory , computational chemistry , chemical physics , materials science , organic chemistry , photochromism , physics , quantum mechanics , composite material
Using the density‐functional vertical self‐consistent reaction field (VSCRF) solvation model, incorporated with the conductor‐like screening model (COSMO) and the self‐consistent reaction field (SCRF) methods, we have studied the solvatochromic shifts of both the absorption and emission bands of four solvent‐sensitive dyes in different solutions. The dye molecules studied here are: S‐TBA merocyanine, Abdel‐Halim's merocyanine, the rigidified aminocoumarin C153, and Nile red. These dyes were selected because they exemplify different structural features likely to impact the solvent‐sensitive fluorescence of “push‐pull”, or merocyanine, fluorophores. All trends of the blue or red shifts were correctly predicted, comparing with the experimental observations. Explicit H‐bonding interactions were also considered in several protic solutions like H 2 O, methanol and ethanol, showing that including explicit H‐bonding solvent molecule(s) in the calculations is important to obtain the correct order of the excitation and emission energies. The geometries, electronic structures, dipole moments, and intra‐ and intermolecular charge transfers of the dyes in different solvents are also discussed.