Sublimable Single Ion Magnets Based on Lanthanoid Quinolinate Complexes: The Role of Intermolecular Interactions on Their Thermal Stability [component]

We report the design, preparation and characterization of two families of thermally robust coordination complexes based on lanthanoid quinolinate compounds: [Ln(5,7-Br 2 q) 4 ]and [Ln(5,7-ClIq) 4 ] -, where q = 8-hydroxyquinoline and Ln = Dy III , Tb III , Er III and Ho III . Samples of [Dy(5,7-Br 2 q) 4 ]decompose upon sublimation, whereas the sodium salt of [Dy(5,7-ClIq) 4 ] -, which displays subtly different crystalline interactions, is sublimable under gentle conditions. The resulting film
more » ... The resulting film presents low roughness with high coverage and the molecular integrity of the coordination complex is verified through AFM, MALDI-TOF, FT-IR and microanalysis. Crucially, the single-molecule magnet behavior exhibited by [Dy(5,7-ClIq) 4 ]in bulk remains detectable by ac magnetometry in the sublimated film. RESULTS AND DISCUSSION Synthesis and structural characterization Low crystallinity or even amorphous samples of both families, Na[Ln(5,7-Br 2 q) 4 ] (1) and Na[Ln(5,7-ClIq) 4 ] (2) (Ln= Dy III , Tb III , Er III and Ho III ), were obtained by direct reaction of the ligand with the corresponding LnCl 3 .6H 2 O salt, as detailed in Supporting Information (Figures S11 and S12) . Recrystallization in DMF resulted in single crystals of Na[Ln(5,7-Br 2 q) 4 ]·DMF (1-DMF) and Na[Ln(5,7-ClIq) 4 ]·DMF (2-DMF). The structure and composition of the
doi:10.1021/acs.inorgchem.8b02080.s001 fatcat:a3s3rcymtfgbpbiecam2rp3tgu