The solution structure and dynamics of metal-bound water exchange have been studied in a series of diastereoisomeric gadolinium complexes of tetra(carboxyethyl) derivatives, of 1,4,7,10-tetraazacyclodecane. The structures of the (RRRS), (RSRS), and (RRSS) ligands and the Eu, Gd, and Tb complexes of the (RRRR) isomer have been determined by X-ray crystallography. Luminescence measurements on the Eu and Tb complexes revealed an integral hydration state (q = 1) in each case for the Eu isomers, whereas nonintegral values were measured for the (RRRR) and (RRRS) Tb isomers (e.g., [(RRRR)-Tb·1] -, q = 0.60). The ratio of the twisted and regular monocapped square antiprismatic isomers has been measured in solution by 1H NMR for the Eu and Tb complexes and followed the order, (RRRR) > (RRRS) > (RSRS) > (RRSS). Water exchange rates in the gadolinium complexe have been determined by 17O NMR and were fastest for the (RRRR) isomer [τ(m) = 68 ns (298 K)] and correlated very well with the proportion of the twisted square anti-prismatic isomer. The rate of water exchange in the (RRRR) Gd complexes is likely to be sufficiently fast so as not to limit the overall relaxivity in higher MW conjugates.

Correlation of water exchange rate with isomeric composition in diastereoisomeric gadolinium complexes of tetra(carboxyethyl)dota and related macrocyclic ligands

AIME, Silvio;BOTTA, Mauro;
2000

Abstract

The solution structure and dynamics of metal-bound water exchange have been studied in a series of diastereoisomeric gadolinium complexes of tetra(carboxyethyl) derivatives, of 1,4,7,10-tetraazacyclodecane. The structures of the (RRRS), (RSRS), and (RRSS) ligands and the Eu, Gd, and Tb complexes of the (RRRR) isomer have been determined by X-ray crystallography. Luminescence measurements on the Eu and Tb complexes revealed an integral hydration state (q = 1) in each case for the Eu isomers, whereas nonintegral values were measured for the (RRRR) and (RRRS) Tb isomers (e.g., [(RRRR)-Tb·1] -, q = 0.60). The ratio of the twisted and regular monocapped square antiprismatic isomers has been measured in solution by 1H NMR for the Eu and Tb complexes and followed the order, (RRRR) > (RRRS) > (RSRS) > (RRSS). Water exchange rates in the gadolinium complexe have been determined by 17O NMR and were fastest for the (RRRR) isomer [τ(m) = 68 ns (298 K)] and correlated very well with the proportion of the twisted square anti-prismatic isomer. The rate of water exchange in the (RRRR) Gd complexes is likely to be sufficiently fast so as not to limit the overall relaxivity in higher MW conjugates.
122(40)
9781
9792
Woods M; Aime S; Botta M; Howard J.A.K; Moloney J.M; Navet M; Parker D; Port M; Rousseaux O
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/102868
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