Lanthanide complexes with polyaminopolycarboxylates as prospective NMR/MRI diagnostic probes: peculiarities of molecular structure, dynamics and paramagnetic properties

The paramagnetic lanthanide complexes with polyaminopolycarboxylate (PAPC) ligands attract considerable attention from the standpoint of potential applications thereof as relaxation agents used in medical magnetic resonance imaging (MRI) and in luminescent materials, as well as owing to promising use thereof as paramagnetic labels for studying the properties of biopolymers since they exhibit thermodynamic stability, good solubility in aqueous media and moderate toxicity. For the last decades, the NMR methods have been used to determine the physical and chemical properties of paramagnetic Ln compounds. The studies concerning paramagnetic NMR lanthanide-induced shifts (LISs) in dissolved Ln complexes, as well as the analysis of band shape as a function of temperature make it possible to obtain valuable information on the structure, intra- and intermolecular dynamics and paramagnetic properties thereof. This review is devoted solely to the following features: firstly, the processes of intramolecular dynamics of lanthanide complexes with polyamino-polycarboxylate ligands such as DOTA, EDTA and DTPA and their derivatives studied by NMR; secondly, the LISs of lanthanide complexes with EDTA, DOTA, DTPA and some of their derivatives depending on temperature and pH. Moreover, in this review, for the first time, the dependence of the activation energy of molecular dynamics in complexes with polydentate ligands on the atomic number of the lanthanide cation is analyzed and a monotonic change in energy is detected, which is due to the effect of lanthanide contraction. It should be noted that this phenomenon is quite general and may also appear in the future in many other series of lanthanide complexes with both other multidentate ligands and with bidentate and monodentate ligands. In the future, it is possible to predict the dependence of the properties of certain lanthanide complexes on the ionic radius of the lanthanide cation based on the approaches presented in the review. In this review, we have also presented the dynamic NMR as the main research method widely used to analyze the processes of molecular dynamics, and the structural studies based on the NMR relaxation spectroscopy and LIS analysis.