TY - JOUR
T1 - Solvent effects on the absorption and emission of [Re(R2bpy)(CO)3X] complexes and their sensitivity to CO2 in solution
AU - Rodríguez, Laura
AU - Ferrer, Montserrat
AU - Rossell, Oriol
AU - Duarte, Filipe J. S.
AU - Gil Santos, A.
AU - Lima, João C.
PY - 2009/5/20
Y1 - 2009/5/20
N2 - The solvatochromic properties of a series of rhenium(I) organometallic compounds have been studied. For this goal, their absorption and emission spectra have been undertaken in a wide range of solvents with different polarity. Kamlet-Taft multiparametric equation and DFT calculations have been used to explain the solvent effect in the MLCT transition of the [Re(R2bpy)(CO)3X] (R = H, t-Bu; X = Cl-, OTf-, C{triple bond, long}CpyRe(R2bpy)(CO)3) complexes. Polarity/polarizability is observed to play an important role in the solvatochromism of the compounds. In spite of this, in general, the splitting of the solvent contributions shows that this effect is not the solely responsible for the observed variations in the energy of this transition and solvent coordination also affects the observed solvatochromism. Compounds with a labile position in the coordination sphere of the metal atom have also been explored in sensorial applications for CO2 detection in solution by means of reversible changes in the recorded emission spectra intensity. The solvent effect on the sensing process is discussed.
AB - The solvatochromic properties of a series of rhenium(I) organometallic compounds have been studied. For this goal, their absorption and emission spectra have been undertaken in a wide range of solvents with different polarity. Kamlet-Taft multiparametric equation and DFT calculations have been used to explain the solvent effect in the MLCT transition of the [Re(R2bpy)(CO)3X] (R = H, t-Bu; X = Cl-, OTf-, C{triple bond, long}CpyRe(R2bpy)(CO)3) complexes. Polarity/polarizability is observed to play an important role in the solvatochromism of the compounds. In spite of this, in general, the splitting of the solvent contributions shows that this effect is not the solely responsible for the observed variations in the energy of this transition and solvent coordination also affects the observed solvatochromism. Compounds with a labile position in the coordination sphere of the metal atom have also been explored in sensorial applications for CO2 detection in solution by means of reversible changes in the recorded emission spectra intensity. The solvent effect on the sensing process is discussed.
KW - CO detection
KW - Electronic spectroscopy
KW - Rhenium
KW - Solvatochromism
KW - TD-DFT
UR - http://www.scopus.com/inward/record.url?scp=67349266956&partnerID=8YFLogxK
U2 - 10.1016/j.jphotochem.2009.03.022
DO - 10.1016/j.jphotochem.2009.03.022
M3 - Article
AN - SCOPUS:67349266956
VL - 204
SP - 174
EP - 182
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
SN - 1010-6030
IS - 2-3
ER -