Experimental assessment of lanthanide ion donor preference:: spectroscopic and theoretical dissection of static charge and dynamic polarisation contributions to axial ligation in a C4-symmetric chiral europium complex

Measurements of the equilibrium constants for ligand exchange (MeCN, 295 K) involving the axial donor in a C-4-symmetric, mono-capped, square antiprismatic cationic Eu complex, supported by calculations based on an electrostatic perturbation model, have been interpreted in terms of a predominant ligand polarisation interaction defined by observation of the hypersensitive DeltaJ = 2 normalised emission intensity, in association with measurements correlating DeltaJ = 1 band splitting and H-1 NMR dipolar shifts that vindicate Bleaney's theory of magnetic anisotropy.