Self-Assembled Heterometallic Complexes by Incorporation of Calcium or Strontium Ion into a Manganese(II) 12-Metallacrown-3 Framework Supported by a Tripodal Ligand with Pyridine-Carboxylate Motifs: Stability in Their Manganese(III) Oxidized Form

We previously reported the multireversible redox behavior of bis(triple‐helicate) pentanuclear complexes of the type [{M(μ‐bpp)3}2M(μ3‐X)]n+ (M=Mn, Fe with X=O and Co with X=OH) with rigid tetradentate binucleating 3,5‐bis(pyridine‐2‐yl)pyrazole (bpp−) ligand. In this article, we focus on the nickel derivative of this family, [{NiII(μ‐bpp)3}2NiII3(μ‐OH)]3+ (13+), which exhibits up to five reversible or quasi‐reversible one‐electron waves in CH3CN solution. The two one‐electron oxidized species as well as the one‐electron reduced species with respective compositions of 4NiII1NiIII (14+), 3NiII2NiIII (15+) and 1NiI4NiII (12+), were quantitatively generated by bulk electrolyses and spectroscopically characterized highlighting the high stability of this family of complexes in several redox states. In addition to the initial complex 13+, the mixed‐valence 12+ was also successfully characterized by single‐crystal X‐ray diffraction, allowing to locate the sites of successive reversible one‐electron events. 12+ is an unusual example of a multinuclear complex including the low‐valent Ni(I) state.

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Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

Gouré

Gerey

Pécaut

et al. 2021

ChemElectroChem

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Chalcogenolato-bridged rhenium(I)-based ester functionalized flexible dinuclear metallacrown ethers: Cation binding, molecular recognition and docking studies

et al. 2022

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Coordination Polymers Ca(II)–Cr(III) and Ba(II)–Cr(III) with Cyclobutane-1,1-dicarboxylic Acid Anions

Bazhina,

Shmelev,

Kiskin

et al. 2024

Russ J Coord Chem

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Self-Assembled Heterometallic Complexes by Incorporation of Calcium or Strontium Ion into a Manganese(II) 12-Metallacrown-3 Framework Supported by a Tripodal Ligand with Pyridine-Carboxylate Motifs: Stability in Their Manganese(III) Oxidized Form

Cited by 3 publications

References 77 publications

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

Chalcogenolato-bridged rhenium(I)-based ester functionalized flexible dinuclear metallacrown ethers: Cation binding, molecular recognition and docking studies

Coordination Polymers Ca(II)–Cr(III) and Ba(II)–Cr(III) with Cyclobutane-1,1-dicarboxylic Acid Anions

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Self-Assembled Heterometallic Complexes by Incorporation of Calcium or Strontium Ion into a Manganese(II) 12-Metallacrown-3 Framework Supported by a Tripodal Ligand with Pyridine-Carboxylate Motifs: Stability in Their Manganese(III) Oxidized Form

Cited by 3 publications

References 77 publications

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the NiII5 and NiINiII4 Redox States

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the NiII5 and NiINiII4 Redox States

Chalcogenolato-bridged rhenium(I)-based ester functionalized flexible dinuclear metallacrown ethers: Cation binding, molecular recognition and docking studies

Coordination Polymers Ca(II)–Cr(III) and Ba(II)–Cr(III) with Cyclobutane-1,1-dicarboxylic Acid Anions

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Product

Resources

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Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States

Multireversible Redox Processes in a Self‐Assembled Nickel Pentanuclear Bis(Triple‐stranded Helicate): Structural and Spectroscopic Characterizations in the Ni^II₅ and Ni^INi^II₄ Redox States