TY - JOUR
T1 - Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers
AU - Nazeeruddin, Mohammad K.
AU - De Angelis, Filippo
AU - Fantacci, Simona
AU - Selloni, Annabella
AU - Viscardi, Guido
AU - Liska, Paul
AU - Ito, Seigo
AU - Takeru, Bessho
AU - Grätzel, Michael
PY - 2005/12/7
Y1 - 2005/12/7
N2 - We report a combined experimental and computational study of several ruthenium(II) sensitizers originated from the [Ru(dcbpyH2) 2(NCS)2], N3, and [Ru(dcbpyH2)(tdbpy)(NCS) 2], N621, (dcbpyH2 = 4,4′-dicarboxy-2,2′- bipyridine, tdbpy = 4,4′-tridecyl-2,2′-bipyridine) complexes. A purification procedure was developed to obtain pure N-bonded isomers of both types of sensitizers. The photovoltaic data of the purified N3 and N621 sensitizers adsorbed on TiO2 films in their monoprotonated and diprotonated state, exhibited remarkable power conversion efficiency at 1 sun, 11.18 and 9.57%, respectively. An extensive Density Functional Theory (DFT)-Time Dependent DFT study of these sensitizers in solution was performed, investigating the effect of protonation of the terminal carboxylic groups and of the counterions on the electronic structure and optical properties of the dyes. The calculated absorption spectra are in good agreement with the experiment, thus allowing a detailed assignment of the UV-vis spectral features of the two types of dyes. The computed alignments of the molecular orbitals of the different complexes with the band edges of a model TiO2 nanoparticle provide additional insights into the electronic factors governing the efficiency of dye-sensitized solar cell devices.
AB - We report a combined experimental and computational study of several ruthenium(II) sensitizers originated from the [Ru(dcbpyH2) 2(NCS)2], N3, and [Ru(dcbpyH2)(tdbpy)(NCS) 2], N621, (dcbpyH2 = 4,4′-dicarboxy-2,2′- bipyridine, tdbpy = 4,4′-tridecyl-2,2′-bipyridine) complexes. A purification procedure was developed to obtain pure N-bonded isomers of both types of sensitizers. The photovoltaic data of the purified N3 and N621 sensitizers adsorbed on TiO2 films in their monoprotonated and diprotonated state, exhibited remarkable power conversion efficiency at 1 sun, 11.18 and 9.57%, respectively. An extensive Density Functional Theory (DFT)-Time Dependent DFT study of these sensitizers in solution was performed, investigating the effect of protonation of the terminal carboxylic groups and of the counterions on the electronic structure and optical properties of the dyes. The calculated absorption spectra are in good agreement with the experiment, thus allowing a detailed assignment of the UV-vis spectral features of the two types of dyes. The computed alignments of the molecular orbitals of the different complexes with the band edges of a model TiO2 nanoparticle provide additional insights into the electronic factors governing the efficiency of dye-sensitized solar cell devices.
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U2 - 10.1021/ja052467l
DO - 10.1021/ja052467l
M3 - Article
C2 - 16316230
AN - SCOPUS:28844470918
SN - 0002-7863
VL - 127
SP - 16835
EP - 16847
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 48
ER -