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![[DPEPhosbcpCu]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)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Four Redox Isomers of a [3 × 3] Copper-Iron Heterometal Grid
Hiroki Sato1, Tatsuya Onuki1, Graham N Newton2
1Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki 305-8571, Japan.
Abstract:
A mixed-valence heterometallic nonanuclear [3 × 3] grid complex, [CuI2CuII6FeIII(L)6](BF4)5·MeOH·9H2O (1; MeOH = methanol), was synthesized by a one-pot reaction of copper and iron ions with multidentate ligand 2,6-bis[5-(2-pyridinyl)-1H-pyrazol-3-yl]pyridine (H2L). 1 showed five quasi-reversible one-electron redox processes centered at +0.74, +0.60, +0.39, +0.27, and -0.13 V versus SCE, assignable to four CuI/CuII processes and one FeII/FeIII couple, respectively. The two-electron-oxidized species [CuII8FeIII(L)6](PF6)7·4MeOH·7H2O (1), the two-electron-reduced species [CuI4CuII4FeIII(L)6](PF6)3·2H2O (1), and the three-electron-reduced species [CuI4CuII4FeII(L)6](PF6)2·5MeOH·H2O (1) were isolated electrochemically. The four redox isomers were characterized by single-crystal X-ray analysis, SQUID magnetometry, and Mössbauer spectroscopy.
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