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NMR study of solution dynamics of LnIII complexes of monophosphorus H4dota analogues
Svítok, Adam ; Hermann, Petr (advisor) ; Dračínský, Martin (referee)
Lanthanides have several specific properties which cannot be found for other elements in the periodic table. Among various applications of lanthanides, complexes of LnIII ions are used in medicine, e.g., as contrast agents in MRI, as luminescent probes or as radiopharmaceuticals, where their specific properties are important. These complexes must be kinetically inert to prevent release of highly toxic "free" LnIII ions. This requirement is fulfilled with pre-organized ligands such as analogues of H4dota (1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). Many of important properties of LnIII complexes of H4dota, such as relaxivity, isomerism and fluxionality, depend on the solution dynamics of the complexes. However, the knowledge of this solution dynamics is limited for LnIII complexes of H4dota derivatives with phosphonate or phosphinate pendant arms. Recently, a new dynamical process where phosphonate oxygen atoms interchange through a bidentate phosphonate intermediate ("a phosphonate rotation") has been proposed by DFT calculations but unconfirmed experimentally. To prove the process experimentally, solution dynamics of LnIII complexes of monophosphonate and monophosphinate derivatives of H4dota was investigated. Especially, to examine the "P-rotation", 17 O NMR spectroscopy was used...
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17O NMR study of LnIIIcomplexes of H4do3apOEt ligand
Svítok, Adam ; Hermann, Petr (advisor) ; Dračínský, Martin (referee)
Macrocyclic complexes of H4dota-like ligands are used in various fields, mainly in medicine. e. g. as MRI contrast agents or luminescent probes. Their applications are greatly influenced by stereochemistry. Stereoisomers of these complexes mostly interconvert with each other in solution. This interconversion can be studied by NMR spectroscopy This work is intended to test 17 O NMR spectroscopy as a tool for monitoring dynamic processes where phosphonate group in the complexes of methylphosphonate derivatives of H4dota is involved. To this end, ligand H4do3apOEt and his LnIII -complexes (Ln ≠ Pm) containing 17 O-labeled phosphonate group were synthesized. Next, 17 O NMR spectra of these complexes were measured and analysed. In an analogy with H4dota complexes, signals of both non-coordinated and coordinated oxygen atoms (except GdIII ) in the complexes could be detected. Fraction of TSA (twisted square-antiprism) and SA (square-antiprism) isomers was determined from the acquired 17 O NMR spectrum for each complex. The determined values were compared with those obtained by analysing 1 H and 31 P NMR spectra of the complexes, which were also measured. The TbIII , DyIII and YbIII complexes (because of high resolution of their 17 O NMR spectra) and CeIII complex (because of anomalous properties of its...
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