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Copper(II) Complexes of Phenolate-Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study
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SYSNO ASEP 0599913 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve SCOPUS Title Copper(II) Complexes of Phenolate-Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study Author(s) Šrein, J. (CZ)
Koláčná, Lucie (UFCH-W) ORCID, RID, SAI
Kotek, J. (CZ)
Kubíček, V. (CZ)
Ludvík, Jiří (UFCH-W) RID, ORCIDArticle number e202400288 Source Title European Journal of Inorganic Chemistry. - : Wiley - ISSN 1434-1948
Roč. 27, č. 31 (2024)Number of pages 12 s. Language eng - English Country US - United States Keywords Copper(II) complexes ; Electrochemistry ; Macrocyclic ligands ; Stability ; UV/VIS spectroscopy Subject RIV CG - Electrochemistry OECD category Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) R&D Projects GA21-23261S GA ČR - Czech Science Foundation (CSF) Method of publishing Limited access Institutional support UFCH-W - RVO:61388955 EID SCOPUS 85206241354 DOI https://doi.org/10.1002/ejic.202400288 Annotation Bis(macrocyclic) complexes are investigated as artificial analogues of natural dinuclear metalloenzymes. Two ligands containing two cyclam rings connected through a p-cresol or 4-nitrophenol spacer were synthesized and their complexing properties were investigated. CuII complexes were prepared and their properties were studied by a combination of spectral, diffraction and electrochemical methods. The phenolate group is not or only weakly coordinated to the central CuII ion and the two macrocycles behave mostly as two independent complexing units. All the determined solid-state structures showed cyclam adopting trans-III geometry, however, solution study indicated the presence of more isomers in the solution whose abundance changes with pH. Electrochemical reduction of the complexes is irreversible and results in the reductive decomplexation to amalgamated Cu metal. The amalgamated metal is re-oxidized to CuII during the anodic scan of CV and the metal ion is re-coordinated. The ligand containing the nitro group shows an irreversible four-electron reduction of the nitro group. The ligands and the complexes undergo also a slow degradation when incubated in the aqueous solutions for a prolonged time. The degradation relies on the “retro-Mannich” cleavage of the methylene bridge connecting the cyclam ring with the phenol moiety. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2025 Electronic address https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202400288
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