The CuII complex of H4TETP (H4TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure (τ = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long Cu–N and a short Cu–O bond; the comparison between powder and solution electronic spectroscopy, the frozen solution EPR spectrum and ligand-field-based calculations (angular overlap model, AOM) indicate that the solution and solid state structures are very similar, i.e. the complex has a relatively low 'in-plane' and a significant axial ligand field with a dx²-y² ground state. The ligand-enforced structure is therefore shown to lead to a partially quenched Jahn–Teller distortion and to a relatively low complex stability, lower than with the corresponding acetate-derived ligand H4TETA. This is confirmed by potentiometric titration and by the biodistribution with 64Cu-labeled ligands which show that the uptake in the liver is significantly increased with the H4TETP-based system.
The preparation and characterization of tris-pyridyl bispidine (3,7-diazabicyclo[3.3.1]nonane) derivatives with benzimidazole and imidazole donor groups at the N-3 position of the bispidine Skeleton and their copper(II) complexes are reported. The impact of the hetaryl substituents on the configurational isomerism of piperidones and their corresponding bispidones has been studied by NMR spectroscopy, revealing the exclusive appearance in the enol form for the piperidones in solution and the trans-configuration regarding the two pyridyl substituents, as well as the sole formation of the unsymmetric exo-endo isomers for the corresponding bispidones. Thus, the bispidones are preorganized ligands for building pentacoordinated complexes, confirmed by the preparation and characterization of the corresponding Cu(II) complexes. Of the di-pyridyl piperidones with benzimidazole and imidazole substituents, and of the Cu(II) complex of the benzimidazole-containing bispidone, Crystals have become available for the analysis by X-ray diffraction, showing that the piperidones form the enol tautomers also in the solid state.