Insights into the Spin Dynamics of Mononuclear Cerium(III) Single-Molecule Magnets

Abstract

Four novel CeIIImononuclear complexes of formulas [Ce(ntfa)3(MeOH)2] (1), [Ce(ntfa)3(5,5′-Me2bipy)] (2), [Ce(ntfa)3(terpy)] (3), and [Ce(ntfa)3(bipy)2] (4), where ntfa = 4,4,4-Trifluoro-1-(naphthalen-2-yl)butane-1,3-dionato, 5,5′-Me2bipy = 5,5′-dimethyl-2,2′-dipyridyl, terpy = 2,2′:6′,2″-Terpyridine, and bipy = 2,2′-bipyridine, have been synthesized and structurally characterized with CeIIIdisplaying coordination numbers of 8, 8, 9, and 10, respectively. Magnetic measurements indicate that all the complexes show a field-induced single-ion magnet behavior under a small applied dc field. The magnetic analysis shows the relevance of the different spin relaxation mechanisms in the magnetic relaxation of the CeIIIcompounds, with special emphasis on the local-mode process. Multiconfigurational calculations were also performed to get more information on the axiality of the compounds.