Magnetic Relaxation in Aluminosilicate Structures Containing Manganese(II) and Gadolinium(III) Complexes

Electron-spin-resonance spectra and nuclear-magnetic-relaxation-dispersion measurements are reported for several aluminosilicate structures to which manganese (II) and gadolinium(III) ions have been added in several structurally distinct ways. EPR spectra demonstrate that diffusion of the hexaaquomanganese(II) ion or the aquogadolinium(III) ion into the zeolite structures is facile, apparently displacing sodium ion or protons. The addition of a complexing agent such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid to the metal-loaded zeolite then yields a complex which in the gadolinium case forms inside the zeolite but in the manganese(II) case forms largely outside the zeolite under our preparation conditions. For the intrazeolite complexes, the gadolinium system is stable to both low pH and high sodium concentrations. The field dependence of the water-proton relaxation displays strong paramagnetic effects that increase with increasing temperature, consistent with exchange limitations on the access of the water-proton spin system to the paramagnetic centers. The shape of the relaxation-dispersion curves demonstrates the importance of anisotropy in the metal-ion EPR spectrum, which leads to a considerable distribution of electron-spin Larmor frequencies and a consequent weak dependence of the nuclear-spin-relaxation rate on the magnetic-field strength.