Analysis of Energy Level Structure and Excited-State Dynamics in a Sm3+ Complex with Soft-Donor Ligands: Sm(Et2Dtc)3(bipy)

Abstract

Using both laser-excited fluorescence and optical absorption methods, we have determined 57 crystal-field (CF) energy levels of Sm 3+ in crystals of Sm(Et2Dtc)3(bipy). The analysis of the energy levels is based on a model Hamiltonian consisting of both free-ion and CF terms. The CF modeling of the experimental energy levels yielded physically reasonable Hamiltonian parameters with a final rms deviation of 17.3 cm(-1). In comparison with Sm 3+ in other hosts, the CF splitting of Sm 3+ in the lattice of Sm(Et2Dtc)3(bipy) is rather weak. The observed fluorescence decay of the 4G(5/2) manifold is single-exponential, with a lifetime of 24.5 mus, indicating only one site of Sm3+ in the lattice. According to the Judd-Ofelt theory, values of three intensity parameters were obtained (Omega(2,4,6) = 1.57, 2.65, and 3.65, in units of 10(-20) cm(-1)). The calculated branching ratios for transitions from the 4G(5/2) manifold are in agreement with experimental values. The calculated radiative lifetime of the 4G(5/2) manifold is 3.24 ms, and the corresponding fluorescence quantum efficiency is only 0.75%. Efficient multiphonon relaxation processes induced by the localized high-frequency vibrational modes in the bipyridyl group may lead to the extremely low quantum efficiency observed. The thermal line broadening and shifts of the 4G(5/2)(1) --> 6F(1/2) transition were observed and fitted very well by the McCumber-Sturge equations with an assumption of Raman phonon scattering processes as the leading relaxation mechanism. The Debye temperature for this crystal is predicted to be 350 K.