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

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 H-1, C-13 and N-15 NMR spectroscopy. The magnitude of the N-15(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.