Electronic Energy Levels and Optical Transitions in Samarium(III) Solvates

Abstract

Lanthanide luminescence fascinates with a complicated electronic structure and "forbidden" transitions. By studying the photophysics of lanthanide(III) solvates, a close to ideal average coordination geometry can be used to map both electronic energy levels and transition probabilities. Some lanthanide(III) ions are simpler to study than others, and samarium(III) belongs to the more difficult ones. The 4f 5 system has numerous absorption and emission lines in the visible and infrared parts of the spectrum and in this work, the energy levels giving rise to these transitions were mapped, the transition probability between them was calculated, and it was shown that the electronic structures of the samarium(III) solvates in DMSO, MeOH, and water are different.

Enabling Molecular-Level Computational Description of Redox and Proton-Coupled Electron Transfer Reactions of Samarium Diiodide

“…Only minor increases in are obtained on the inclusion of continuum solvation effects (for THF) and coordinating iodide, water, and hydroxide ligands in the calculations. Limited environmental influence on the SOC-induced stabilization is also indicated by the levels of the Sm 3+ 6 H o term observed in various solvents 55 , 56 being comparable to those of Sm 3+ ions in LaCl 3 . 54…”

“…54 More importantly, the differential stabilization of | | are obtained on the inclusion of continuum solvation effects (for THF) and coordinating iodide, water, and hydroxide ligands in the calculations. Limited environmental influence on the SOCinduced stabilization is also indicated by the levels of the Sm 3+ 6 H o term observed in various solvents 55,56 being comparable to those of Sm 3+ ions in LaCl 3 . 54 In conclusion, due to the limited influence of the environment on the SOC ground-state stabilization, we adopt the stabilization derived from the atomic spectra of Sm 2+ and Sm 3+ ions.…”

Heteroleptic samarium complexes with high quantum yields for temperature sensing applications

“…These bands are assigned as 6 F 1/2 (883 nm), 6 H 13/2 (909 nm), 6 F 3/2 (928 nm), 6 F 5/2 (949 nm), 6 F 7/2 (1034 nm), 6 F 9/2 (1183 nm), and 6 F 11/2 (1420 nm). The peak around 1295 nm could not be assigned, and Sørensen et al 50 considered this peak as measuring artefacts of the spectrophotometer. The band shape of 4f-4f transitions of eight-coordinate complex (1) differs from nine-coordinate complex (2), and this could be due to structural differences between both the samarium complexes.…”

Crystal structures of two SmIII complexes with dipicolinate [DPA]2− ligands: comparison of luminescent properties of products obtained at different pH values

“…doublets defined by AEm J values, can be observed from the luminescence spectra (Cheisson & Schelter, 2019;Wybourne, 2004;Chen et al, 2005;Mortensen et al, 2022;Carnall et al, 1968). Because Sm III is a Kramers cation, it has an uneven number of electrons (4f 5 ) and all states will be double degenerate without the presence of a magnetic field (Eliseeva & Bu ¨nzli, 2010).…”