The electronic structure of organometallic complexes of the f elements—XIV. Quantitative interpretation of the luminescence and magnetochemical properties of Cp 3Pr·CNC 6H 11

Abstract

The 3 P 0 → 3 H 5 transition can be observed in the low temperature pre-resonance luminescence spectrum of the cyclobexylisocyanide adduct of tris (η 5-cyclopentadienyl)-praseodymium(III). The previously assigned crystal field splitting pattern, completed by the levels which are derived from the 3 H 5 term, was fitted to the parameters of a semiempirical Hamiltonian with an rms deviation of 34.5 cm −1 for 48 levels. From the eigenvalues and eigenfunctions obtained, the experimentally determined temperature dependence of the paramagnetic susceptibility could be reproduced by introducing orbital reduction factors between 0.975 and 1.0. The experimental temperature dependence of the 1H-NMR shift of the α proton of the cyclohexyl ring could be simulated by considering only the dipolar contribution.