Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 130, Issue 43, Pages 14329-14338Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja805498w
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Funding
- Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy [DE-FG02-07ER15909]
- NERSC
- NSF [CHE-0215926, 0404191]
- Directorate For Engineering
- Div Of Electrical, Commun & Cyber Sys [0404191] Funding Source: National Science Foundation
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A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering pholocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2':6,2 ''-terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II)-->Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.
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