Magnetic properties and neutron spectroscopy of lanthanoid-{tetrabromocatecholate/18-crown-6} single-molecule magnets

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dc.contributor.authorDunstan, MAen_AU
dc.contributor.authorCagnes, MPen_AU
dc.contributor.authorPhonsri, Wen_AU
dc.contributor.authorMurray, KSen_AU
dc.contributor.authorMole, RAen_AU
dc.contributor.authorBoskovic, Cen_AU
dc.date.accessioned2024-12-19T03:03:56Zen_AU
dc.date.available2024-12-19T03:03:56Zen_AU
dc.date.issued2022-03-14en_AU
dc.date.statistics2024-09-25en_AU
dc.description.abstractLanthanoid single-molecule magnets (Ln-SMMs) exhibit slow magnetic relaxation at low temperatures. This arises from an energy barrier to magnetisation reversal associated with the crystal field (CF) splitting of the Ln(III) ion. The magnetic relaxation is impacted by the interaction of the molecule with the crystal lattice, so factors including particle size and crystal packing can play an important role. In this work, a family of compounds of general formula [Ln(18-c-6)(NO3)(Br4Cat)]·X (Ln = La, Tb, Dy; 18-c-6 = 18-crown-6; Br4Cat2− = tetrabromocatecholate) has been studied by inelastic neutron scattering (INS) and magnetometry to elucidate the effects of crystal packing on the slow magnetic relaxation of the Tb(III) and Dy(III) compounds. The deuterated analogues [Ln(18-c-6-d24)(NO3)(Br4Cat)]·CH3CN-d3 (1-LnD; Ln = La, Tb, Dy) have been synthesised, with 1-TbD and the diamagnetic analogue 1-LaD measured by INS. The dynamic magnetic properties of 1-TbD and 1-DyD have also been measured and compared for two samples with different particle sizes. To probe packing effects on the slow magnetic relaxation, two new solvatomorphs of the hydrogenous compounds [Ln(18-c-6)(NO3)(Br4Cat)]·X (2-Ln: X = CH2Cl2; 3-Ln: X = 0.5 toluene) have been obtained for Ln = Tb and Dy. The CF splitting between the ground and first excited CF pseudo-doublets has been experimentally determined for 1-TbD by INS, and strongly rare earth dependent and anharmonic lattice vibrational modes have also been observed in the INS spectra, with implications for slow magnetic relaxation. Dynamic magnetic measurements reveal significant particle-size dependence for the slow magnetic relaxation for 1-TbD, while a previously reported anomalous phonon bottleneck effect in the 1-DyD analogue does not change with particle size. Further dynamic magnetic measurements of 2-Ln and 3-Ln show that the slow magnetic relaxation in these Ln-SMMs is strongly dependent on lattice effects and crystal packing, which has implications for the future use of Ln-SMMs in devices. © 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing.en_AU
dc.description.sponsorshipM. A. D. acknowledges support from an AINSE Post-Graduate Research Award and the Australian Government for a Research Training Program stipend. C. B., R. A. M., and K. S. M. thank the Australian Research Council for funding (DP170100034 and FT190100293). The authors would like to thank AINSE and ANSTO (P6363 & NDF6364) for access funding.en_AU
dc.identifier.citationDunstan, M. A., Cagnes, M., Phonsri, W., Murray, K. S., Mole, R. A., & Boskovic, C. (2022). Magnetic properties and neutron spectroscopy of lanthanoid-{tetrabromocatecholate/18-crown-6} single-molecule magnets. Australian Journal of Chemistry, 75(9), 595-609. doi:10.1071/CH21306en_AU
dc.identifier.issn0004-9425en_AU
dc.identifier.issn1445-0038en_AU
dc.identifier.issue9en_AU
dc.identifier.journaltitleAustralian Journal of Chemistryen_AU
dc.identifier.pagination595-609en_AU
dc.identifier.urihttps://doi.org/10.1071/ch21306en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/15833en_AU
dc.identifier.volume75en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherCSIRO Publishingen_AU
dc.subjectMagnetic propertiesen_AU
dc.subjectNeutron spectroscopyen_AU
dc.subjectMoleculesen_AU
dc.subjectMagnetsen_AU
dc.subjectTemperature rangeen_AU
dc.subjectMagnetismen_AU
dc.subjectCrystalsen_AU
dc.subjectDeuterationen_AU
dc.subjectInelastic scatteringen_AU
dc.subjectRare earthsen_AU
dc.subjectSpectroscopyen_AU
dc.titleMagnetic properties and neutron spectroscopy of lanthanoid-{tetrabromocatecholate/18-crown-6} single-molecule magnetsen_AU
dc.typeJournal Articleen_AU
dcterms.dateAccepted2022-01-12en_AU
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