Electronic structure of the high symmetrical compounds of f-element. Part 33. A novel experimental crystallized trigonal-bipyramidal coordinated lanthanide(III) systems: Pr[N(SiMe3)2](CNR)2 (R = tBu, C6H11)]

The absorption und magnetic circular dichroism spectra of the dissolved trigonal-bipyramidal complex PrN(SiMe3)2]3(CNtBu)2 (1) as well as the luminescence and absorption spectra of both solid 1 and solid PrN(SiMe3)2]3(CNC6H11)2 (2) (pellets, unoriented single crystals) were measured at ambient and low temperatures. Because of the violation of the selection rules for D3h symmetry by both compounds a reliable crystal field(CF) splitting pattern for the ground manifold 3H4, but only a plausible for the f 2 configuration could be derived on the basis of these measurements. The latter could be simulated with a reduced r.m.s. deviation of 32.6 cm(-1) for 29 assignments by fitting the free parameters of a phenomenological Hamiltonian. The adequacy of the calculated wavefunctions of this fit in the low energy range is proved by the excellent agreement of calculated and experimental temperature dependence of mu2(eff) for compound 1. The CF parameters of this fit are considered as a "master set" of CF parameters for future CF analyses of the electronic structures of trigonal bipyramidally coordinated lanthanide(III) systems.