Fluorination effects on rotational correlation times of tris(ß-diketonato)aluminum(III) in CO2 by 27Al NMR relaxation measurements.

(27)Al NMR longitudinal relaxation times, T(1,obs)((27)Al), of [Al(acac)(3)] and [Al(hfa)(3)] (Hacac = acetylacetone, Hhfa = hexafluoroacetylacetone) in CH(3)CN and CO(2) were measured over a wide range of temperature and pressure. The rotational correlation times, τ(r), of the tris(ß-diketonato)aluminum(III) complexes were determined from T(1,obs)((27)Al) using (27)Al quadrupole coupling constants, eQq/h((27)Al), which were also obtained to be 3.11 and 3.22 MHz for [Al(acac)(3)] and [Al(hfa)(3)], respectively, in CD(3)CN by the dual spin probe technique in the present study. At each temperature, τ(r) increased almost linearly with increasing viscosity, η, in both CH(3)CN and CO(2); however, τ(r) in CO(2) at near critical densities deviated appreciably upward, as shown in a similar analogue of bis(acetylacetonato)beryllium(II), [Be(acac)(2)] (Umecky; et al. J. Phys. Chem. B 2002, 106, 11114). The η/T dependence of τ(r) was examined to discuss intermolecular interactions between the complexes and solvent molecules in terms of the fluorination and geometrical effects. The degree of solute-solvent interactions increases in the order [Be(acac)(2)] < [Al(hfa)(3)] < [Al(acac)(3)] in CH(3)CN and [Al(acac)(3)] < [Be(acac)(2)] < [Al(hfa)(3)] in CO(2). The results suggest that dipolar CH(3)CN molecules interact with negatively charged oxygen atoms in the complexes, whereas nonpolar CO(2) prefers fluorinated substituents as well as quasi-aromatic rings in the ligands. Moreover, the relationship between the rotational and translational motions of tris(acetylacetonato)metal(III), [M(III)(acac)(3)], in CO(2) was investigated.