EPR investigations of mesoporous silica doped with metal transitions ions

Electron paramagnetic resonance (EPR) experiments were performed on mesoporous silica powders in which (1,4,8,11-tetraazacyclotetradecane) cyclam groups were incorporated. These functionalised groups allow an easy binding with copper and nickel ions. Comparative studies are carried out on samples functionalised by cyclam groups located either inside the pores or in the walls of the mesoporous structures. Copper and nickel EPR parameters, including g-tensors and hyperfine components are determined and relevant electronic, magnetic and structural information are obtained. The EPR spectra intensities and line-widths are investigated on the temperature range [4 K,300 K] to clarify the relative dispersion or agglomeration of the doping ions in the matrices as well as their possible thermally activated mobility and ions pairing. As a support of the experimental EPR investigations, numerical simulations of the geometry of metallic ion environments and their electronic properties are carried out and discussed. The possibility of dynamic Jahn Teller (JT) effect in the temperature range [200, 60 K] is discussed for the nickel doped matrices where the low temperature quenched JT configuration is thought to favour the formation of Ni3+ pairs.