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Interfacial Electron Transfer in Metal Cyanide-Sensitized TiO_2 Nanoparticles

Harris, James A. and Trotter, Kevin and Brunschwig, Bruce S. (2007) Interfacial Electron Transfer in Metal Cyanide-Sensitized TiO_2 Nanoparticles. Journal of Physical Chemistry B, 111 (24). pp. 6695-6702. ISSN 1520-6106. doi:10.1021/jp0679313.

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Electroabsorption (Stark) spectroscopy has been used to study the charge-transfer absorption from a transition-metal−cyanide complex to a TiO_2 nanoparticle. Transition-metal cyanide/TiO_2(particle) systems were synthesized using Fe^(II)(CN)_6^(4-), Ru^(II)(CN)_6^(4-), Mo^(IV)(CN)_8^(4-), and W^(IV)(CN)_8^(4-). On formation of the M(CN)_n^(4-)/TiO_2(particle) system, a new metal-to-particle charge-transfer (MPCT) absorption band is observed in the 390−480 nm region. Analysis of the absorption spectra suggests that the TiO_2 level involved in the MPCT transition resides at significantly higher energy than the bottom of the conduction band and that the electronic coupling between the two metal centers is the dominant factor determining the position of the MPCT band maximum. The average charge-transfer distances determined by Stark spectra range from 4.1−4.7 Å. The observation of relatively short charge-transfer distances leads to the conclusion that the MPCT absorption is from the transition-metal cyanide center to a level that is localized on the Ti atom bound to a nitrogen end of the [O_2Ti−N−C−M(CN)_x] system. The electronic coupling, H_(ab), calculated for a two state model is similar to values observed in dinuclear metal complexes.

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Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2007 American Chemical Society. Received 29 November 2006. Published online 3 April 2007. Published in print 1 June 2007. B.S.B. acknowledges Dr. Norman Sutin's encouragement to build a Stark spectrometer and undertake studies of charge-transfer compounds using it. Specifically, we would like to thank him for detailed discussions and very helpful advice on this manuscript. We also thank Professor Harry B. Gray for the generous donation of K_4[W^(IV)(CN)_8]·H_2O and K_4[Mo^(IV)(CN)_8]·2H_2O. This work was supported by the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology and the National Science Foundation. Note Added after ASAP Publication. This article was posted ASAP on April 3, 2007. Figure 1 has been revised. The corrected version was posted on May 30, 2007.
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Caltech Beckman InstituteUNSPECIFIED
Issue or Number:24
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Official Citation:Interfacial Electron Transfer in Metal Cyanide-Sensitized TiO2 Nanoparticles James A. Harris, Kevin Trotter, and Bruce S. Brunschwig The Journal of Physical Chemistry B 2007 111 (24), 6695-6702 DOI: 10.1021/jp0679313
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78975
Deposited By: Ruth Sustaita
Deposited On:12 Jul 2017 17:27
Last Modified:15 Nov 2021 17:44

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