Intermolecular energy transfer across nanocrystalline semiconductor surfaces

被引:26
作者
Higgins, GT
Bergeron, BV
Hasselmann, GM
Farzad, F
Meyer, GJ [1 ]
机构
[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA
[2] Johns Hopkins Univ, Dept Mat Sci & Engn, Baltimore, MD 21218 USA
关键词
D O I
10.1021/jp0543680
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The yields and dynamics for energy transfer from the metal-to-ligand charge-transfer excited states of Ru(deeb)(bpy)(2)(PF6)(2), Ru2+, and Os(deeb)(bpy)(2)(PF6)(2), OS2+, where deeb is 4,4'-(CH3CH2CO2)(2)-2,2'-bipyridine, anchored to mesoporous nanocrystalline (anatase) TiO2 thin films were quantified. Lateral energy transfer from Ru2+* to Os2+ was observed, and the yields were measured as a function of the relative surface coverage and the external solvent environment (CH3CN, THF, CCl4, and hexanes). Excited-state decay of Ru2+*/TiO2 was well described by a parallel first- and second-order kinetic model, whereas OS2+*/TiO2 decayed with first-order kinetics within experimental error. The first-order component was assigned to the radiative and nonradiative decay pathways (tau = 1 mu s for Ru2+*/TiO2 and tau = 50 ns for OS2+*/TiO2). The second-order component was attributed to intermolecular energy transfer followed by triplet-triplet annihilation. An analytical model was derived that allowed determination of the fraction of excited-states that follow the two pathways. The fraction of Ru2+*/TiO2 that decayed through the second-order pathway increased with surface coverage and excitation intensity. Monte Carlo simulations were performed to estimate the RU2+* -> Ru2+ intermolecular energy transfer rate constant of (30 ns)(-1).
引用
收藏
页码:2598 / 2605
页数:8
相关论文
共 29 条
[1]   Determination of triplet quantum yields from triplet-triplet annihilation fluorescence [J].
Bachilo, SM ;
Weisman, RB .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (33) :7711-7714
[2]   Luminescent and redox-active polynuclear transition metal complexes [J].
Balzani, V ;
Juris, A ;
Venturi, M ;
Campagna, S ;
Serroni, S .
CHEMICAL REVIEWS, 1996, 96 (02) :759-833
[3]   Thin film actinometers for transient absorption spectroscopy: Applications to dye-sensitized solar cells [J].
Bergeron, BV ;
Kelly, CA ;
Meyer, GJ .
LANGMUIR, 2003, 19 (20) :8389-8394
[4]   ESTIMATION OF EXCITED-STATE REDOX POTENTIALS BY ELECTRON-TRANSFER QUENCHING - APPLICATION OF ELECTRON-TRANSFER THEORY TO EXCITED-STATE REDOX PROCESSES [J].
BOCK, CR ;
CONNOR, JA ;
GUTIERREZ, AR ;
MEYER, TJ ;
WHITTEN, DG ;
SULLIVAN, BP ;
NAGLE, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (17) :4815-4824
[5]   LIFETIMES, SPECTRA, AND QUENCHING OF THE EXCITED-STATES OF POLYPYRIDINE COMPLEXES OF IRON(II), RUTHENIUM(II), AND OSMIUM(II) [J].
CREUTZ, C ;
CHOU, M ;
NETZEL, TL ;
OKUMURA, M ;
SUTIN, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (04) :1309-1319
[6]   An antenna polymer for visible energy transfer [J].
Dupray, LM ;
Devenney, M ;
Striplin, DR ;
Meyer, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (42) :10243-10244
[7]   Competitive intermolecular energy transfer and electron injection at sensitized semiconductor interfaces [J].
Farzad, F ;
Thompson, DW ;
Kelly, CA ;
Meyer, GJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (23) :5577-5578
[8]   Energy transfer between Ru(II) and Os(H) polypyridyl complexes linked to polystyrene [J].
Fleming, CN ;
Dupray, LM ;
Papanikolas, JM ;
Meyer, TJ .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (10) :2328-2334
[9]   Ultrafast excited-state energy migration dynamics in an efficient light-harvesting antenna polymer based on Ru(II) and Os(II) polypyridyl complexes [J].
Fleming, CN ;
Maxwell, KA ;
DeSimone, JM ;
Meyer, TJ ;
Papanikolas, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (42) :10336-10347
[10]   Photoelectrochemical cells [J].
Grätzel, M .
NATURE, 2001, 414 (6861) :338-344