Four Redox Isomers of a [3 × 3] Copper–Iron Heterometal Grid

A mixed-valence heterometallic nonanuclear [3 × 3] grid complex, [CuI 2CuII 6FeIII(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-reversib...

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Bibliographic Details
Published in:Inorganic chemistry 2023-11, Vol.62 (44), p.18003-18008
Main Authors: Sato, Hiroki, Onuki, Tatsuya, Newton, Graham N., Shiga, Takuya, Oshio, Hiroki
Format: Article
Language:English
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Summary:A mixed-valence heterometallic nonanuclear [3 × 3] grid complex, [CuI 2CuII 6FeIII(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 [CuII 8FeIII(L)6]­(PF6)7·4MeOH·7H2O (1 2eOx ), the two-electron-reduced species [CuI 4CuII 4FeIII(L)6]­(PF6)3·2H2O (1 2eRed ), and the three-electron-reduced species [CuI 4CuII 4FeII(L)6]­(PF6)2·5MeOH·H2O (1 3eRed ) were isolated electrochemically. The four redox isomers were characterized by single-crystal X-ray analysis, SQUID magnetometry, and Mössbauer spectroscopy.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.3c02498