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Lanthanide Complexes with 1H paraCEST and 19F Response for Magnetic Resonance Imaging Applications
{We present a detailed study of the lanthanide(III) complexes with cyclen-based ligands containing phenylacetamide pendants that incorporate CF3 group(s) at different distances from the metal ion. The complexes exhibit square-antiprismatic coordination in solution, as demonstrated by analysis of the Yb3+-induced paramagnetic shifts and the X-ray structure of the [YbL3] complex. Luminescence lifetime measurements and a detailed 1H and 17O relaxometric characterization confirmed the presence of an inner-sphere H2O molecule. The Tm3+ complexes provide chemical-exchange saturation-transfer response upon saturation at the frequency of the amide protons. A 19F relaxation study provided accurate estimates of the Ln\mbox{$\cdot$}\mbox{$\cdot$}\mbox{$\cdot$}F distances that were used to rationalize the efficiency of the complexes as 19F magnetic resonance imaging (MRI) probes, which was tested in vitro using MRI phantom studies.}
@article{item_3055592, title = {{Lanthanide Complexes with 1H paraCEST and 19F Response for Magnetic Resonance Imaging Applications}}, journal = {{Inorganic Chemistry}}, abstract = {{We present a detailed study of the lanthanide(III) complexes with cyclen-based ligands containing phenylacetamide pendants that incorporate CF3 group(s) at different distances from the metal ion. The complexes exhibit square-antiprismatic coordination in solution, as demonstrated by analysis of the Yb3+-induced paramagnetic shifts and the X-ray structure of the [YbL3] complex. Luminescence lifetime measurements and a detailed 1H and 17O relaxometric characterization confirmed the presence of an inner-sphere H2O molecule. The Tm3+ complexes provide chemical-exchange saturation-transfer response upon saturation at the frequency of the amide protons. A 19F relaxation study provided accurate estimates of the Ln\mbox{$\cdot$}\mbox{$\cdot$}\mbox{$\cdot$}F distances that were used to rationalize the efficiency of the complexes as 19F magnetic resonance imaging (MRI) probes, which was tested in vitro using MRI phantom studies.}}, volume = {58}, number = {11}, pages = {7571--7583}, publisher = {American Chemical Society}, address = {Washington, DC}, year = {2019}, slug = {item_3055592}, author = {Pujales-Paradela, R and Savi\'c, T and P\'erez-Lourido, P and Esteban-G\'omez, D and Angelovski, G and Botta, M and Platas-Iglesias, C} }