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![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
The cation radicals of free base and zinc bacteriochlorin, bacteriochlorophyll, and bacteriopheophytin
1Department of Applied Science, Brookhaven National Laboratory, Upton, New York 11973.
Abstract:
One-electron oxidation of zinc tetraphenylbacteriochlorin and its metal-free base yielded stable cation radicals. Electron spin resonance hyperfine splittings were assigned by selective deuterations. These results indicate that the protons of the saturated rings of the bacteriochlorins carry large spin densities, in accord with molecular orbital calculations. Comparison in vitro of the optical spectra of bacteriochlorins and their cation radicals with those of bacteriochlorophyll show close correspondence and suggest that the electron spin resonance data from the former may also prove a guide to the biological molecule. The surprising similarity in properties between the radicals of free base and zinc bacteriochlorins is maintained in the chlorophylls: cation radicals of bacteriopheophytin and methyl pheophorbide (the free bases of bacteriochlorophyll and methyl chlorophyllide, respectively) exhibit electron spin resonance properties similar to those of their magnesium-containing derivatives. The possibility that metal-free chlorophylls participate in photosynthesis is discussed.
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