Hill, Craig L. and Kozik, Mariusz and Winkler, Jay and Hou, Yuqi and Prosser-McCartha, Christina M. (1993) Polyoxometalates in Catalytic Photochemical Hydrocarbon Functionalization and Photomicrolithography. In: Photosensitive Metal-Organic Systems. Advances in Chemistry. No.238. American Chemical Society , Washington, DC, pp. 243-259. ISBN 9780841225275. https://resolver.caltech.edu/CaltechAUTHORS:20180405-140056021
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Abstract
The energetic and mechanistic features of catalytic photochemical oxidation of organic substrates by polyoxometalates and then the applications of this chemistry to catalytic alkane functionalization, microlithography, and catalytic dehalogenation are succinctly reviewed Three sets of experiments that affect these areas are presented, and the future development of catalytic photoredox processes effected by polyoxometalates is discussed The excited state of decatungstate, W_(10)O_(32)^(4-) (1), and the conventional ground-state radical, tert-BuO·, have similar reactivities and lead to similar products upon reaction with various organic substrates. The simultaneous photooxidation of cyclooctane and tetrahydrofuran leads to some cross-coupling product and a complex organic product distribution that is consistent to a large degree with intermediate freely diffusing radicals. Laser flash photolysis measurements (355-nm frequency tripled Nd:YAG output of the heretofore unreported emission of 1 (λ_(max) = 615 nm) establish that the lifetime of the excited state (1^*) is 21 ± 3 ps at 25 °C in 9:1 acetonitrile—water solution.
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| Additional Information: | © 1993 American Chemical Society. Received for review November 7, 1991. Accepted revised manuscript May 18, 1992. Published in print 5 May 1993. Research performed at Emory University was supported by National Science Foundation (Grant No. CHE-9022317) and the Army Research Office (Grant No. DAAL03-91-G-0021), and research performed at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. | |||||||||
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| Series Name: | Advances in Chemistry | |||||||||
| Issue or Number: | 238 | |||||||||
| DOI: | 10.1021/ba-1993-0238.ch013 | |||||||||
| Record Number: | CaltechAUTHORS:20180405-140056021 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180405-140056021 | |||||||||
| Official Citation: | Polyoxometalates in Catalytic Photochemical Hydrocarbon Functionalization and Photomicrolithography Craig L. Hill, Mariusz Kozik, Jay Winkler, Yuqi Hou, and Christina M. Prosser-McCartha Photosensitive Metal—Organic Systems. May 5, 1993, 243-259 DOI:10.1021/ba-1993-0238.ch013 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 85651 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 05 Apr 2018 21:51 | |||||||||
| Last Modified: | 15 Nov 2021 20:30 |
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