Structural Elucidation, Aggregation, and Dynamic Behaviour of N,N,N,N -Copper(I) Schiff Base Complexes in Solid and in Solution: A Combined NMR, X-ray Spectroscopic and Crystallographic Investigation.

Autor: Gerz I; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Jannuzzi SAV; Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstraße 34-36 45470 Mülheim an der Ruhr Germany., Hylland KT; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Negri C; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Wragg DS; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Øien-Ødegaard S; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Tilset M; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., Olsbye U; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway., DeBeer S; Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstraße 34-36 45470 Mülheim an der Ruhr Germany., Amedjkouh M; Department of Chemistry University of Oslo P. O. Box 1033 Blindern 0315 Oslo Norway.; Centre for Materials Science and Nanotechnology University of Oslo P.O. Box 1126 Blindern 0316 Oslo Norway.
Jazyk: angličtina
Zdroj: European journal of inorganic chemistry [Eur J Inorg Chem] 2021 Dec 14; Vol. 2021 (46), pp. 4762-4775. Date of Electronic Publication: 2021 Oct 29.
DOI: 10.1002/ejic.202100722
Abstrakt: A series of Cu(I) complexes of bidentate or tetradentate Schiff base ligands bearing either 1- H -imidazole or pyridine moieties were synthesized. The complexes were studied by a combination of NMR and X-ray spectroscopic techniques. The differences between the imidazole- and pyridine-based ligands were examined by 1 H, 13 C and 15 N NMR spectroscopy. The magnitude of the 15 N imine coordination shifts was found to be strongly affected by the nature of the heterocycle in the complexes. These trends showed good correlation with the obtained Cu-N imine bond lengths from single-crystal X-ray diffraction measurements. Variable-temperature NMR experiments, in combination with diffusion ordered spectroscopy (DOSY) revealed that one of the complexes underwent a temperature-dependent interconversion between a monomer, a dimer and a higher aggregate. The complexes bearing tetradentate imidazole ligands were further studied using Cu K-edge XAS and VtC XES, where DFT-assisted assignment of spectral features suggested that these complexes may form polynuclear oligomers in solid state. Additionally, the Cu(II) analogue of one of the complexes was incorporated into a metal-organic framework (MOF) as a way to obtain discrete, mononuclear complexes in the solid state.
Competing Interests: The authors declare no conflict of interest.
(© 2021 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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