Simultaneous aluminium oxide pillaring and copper(II) Schiff base complexes encapsulation in a montmorillonite

Copper(II) acetylacetonate and two complexes with pentadentate N3O2 Schiff-base ligands derived from acetylacetone - bis(acetylacetonate)-3-amino-bis(propyldiimine), ([Cu(acac)(2)trien]), and bis( acetylacetonate)-3-methylamino- bis(propyldiimine), [Cu(acac)(2)Metrien], were encapsulated into a pillared clay (PILC) using a new methodology that involves simultaneous oligomer pillaring and complex encapsulation: in the present work the pillaring oligomer was [Al13O4(OH)(24+x)(H2O)(12-x)]((7-x)+) and the starting clay was a Portuguese montmorilonite. All the materials were characterised by X-ray photoelectron spectroscopy, powder X-ray diffraction, adsorption of nitrogen at low temperature and infrared spectroscopy and, for copper-based materials, by chemical analysis. Data indicate that all three complexes have been immobilised within the matrix, but only for [Cu(acac)(2)] and [Cu(acac)(2)trien], did metal complex immobilisation take place concomitantly with aluminium pillar intercalation. Furthermore, the encapsulation of the latter complexes induced an increase in the PILC basal distance when compared with the pillared clay prepared without complex present. Finally, in all the materials the encapsulated complexes exhibit structural properties that are different from those of the free complexes, a consequence of the steric effects imposed by the porous structure of the PILC.