Structure and Dynamics of a Trinuclear Gadolinium(III) Complex: The Effect of Intramolecular Electron Spin Relaxation on Its Proton Relaxivity(1).
The trinuclear [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) complex has been characterized in aqueous solution as a model compound from the point of view of MRI: the parameters that affect proton relaxivity have been determined in a combined variable temperature, pressure, and multiple-field (17)O NMR, EPR, and NMRD study. The solution structure of the complex was found to be the same as in solid state: the total coordination number of the lanthanide(III) ion is 8 with two inner-sphere water molecules. EPR measurements proved a strong intramolecular dipole-dipole interaction between Gd(III) electron spins. This mechanism dominates electron spin relaxation at high magnetic fields (B > 5 T). Its proportion to the overall relaxation decreases with decreasing magnetic field and becomes a minor term at fields used in MRI. Consequently, it cannot increase the electronic relaxation rates to such an extent that they limit proton relaxivity. [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) undergoes a relatively slow water exchange (k(ex)(298) = (1.1 +/- 0.2) x 10(7) s(-1)) compared to the Gd(III) aqua ion, while the mechanism is much more associatively activated as shown by the activation volume (DeltaV () = (-12.7 +/- 1.5) cm(3) mol(-)(1)). The lower exchange rate, as compared to [Gd(H(2)O)(8)](3+) and [Gd(PDTA)(H(2)O)(2)](-), can be explained with the higher rigidity of the [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) which considerably slows down the transition from the eight-coordinate reactant to the nine-coordinate transition state. The unexpectedly low rotational correlation time of the complex is interpreted in terms of a spherical structure with a large hydrophobic surface avoiding the formation of a substantial hydration sphere around [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+).
Tóth É
Éva
Institute of Inorganic and Analytical Chemistry, University of Lausanne, Switzerland, Laboratorium für Anorganische Chemie, ETH-Zentrum, Zürich, Switzerland, Universität des Saarlandes, Fachrichtung Anorganische Chemie, Saarbrücken, Germany, and Department of Experimental Physics, Technical University of Budapest, Hungary.
Helm
Lothar
L
Merbach
André E.
AE
Hedinger
Roman
R
Hegetschweiler
Kaspar
K
Jánossy
András
A