The Pursuit of High Blocking Temperature Single Molecule Magnets using 4f/5f Cyclooctatetraenyl Complexes
Creators: name: Le Roy, Jennifer
Publisher: name: Université d'Ottawa / University of Ottawa
Year: 2015
Subjects: Single-molecule magnet
Lanthanide
Uranium
Blocking temperature

description: This dissertation describes the single-molecule magnet (SMM) behaviour of f-block cyclooctatetraenyl sandwich complexes. Chapter one introduces the concepts that dictate SMM behavior particularly in f-elements. The emphasis is to understand the origin of magnetic behaviour and the properties that make lanthanide elements particularly interesting to explore. Current strategies used to predict such behaviour are discussed and a literature review on the subject is provided. Chapter Two describes the magnetic properties of eight isostructural lanthanide sandwich complexes utilizing 1,4-bis(trimethylsilyl)cyclooctatetraenyl dianion as the ligand, [Li(DME)3][LnIII(COT”)2] (Ln = Ce, Nd, Gd, Tb, Dy, Ho, Er, Tb, COT” = 1,4-bis(trimethylsilyl)cyclooctatetraenyl dianion, DME = dimethoxyethane). The complexes display a wide range of magnetic behaviour. The best performing SMM was the erbium complex, which had a blocking temperature of 8 K. Investigating different lanthanide ions with the same ligand enabled us to evaluate our findings in relation to current models used to predict SMM behaviour in lanthanide complexes. Chapter three extends the discussion of lanthanide sandwich complexes to include higher symmetry cyclooctatetraenyl complexes of ErIII and DyIII, [K(18-C-6)][LnIII(COT)2] (18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane, COT = cyclooctatetraene).The change in symmetry evoked by removing the trimethylsyl- (TMS) groups on the ligand greatly influenced the magnetic properties of both complexes. Ab initio calculations revealed that the magnetic relaxation in the ErIII complex occurs via the second excited state which contributes to the very high blocking temperature of 10 K in this complex. Chapter four presents an organometallic building block approach to create triple decker lanthanide COT” complexes of GdIII, DyIII and ErIII with a molecular formula of LnIII2(COT”)3. Synthetically, we couple together the sandwich complexes discussed in Chapter 2 by oxidatively removing one ligand to produce linear complexes where the two metals are bridged by an aromatic COT” ligand. The magnetic properties of all complexes are compared to their respective mononuclear analogs. Most interesting is the unprecedented 4 K increase in blocking temperature of the triple decker ErIII analog compared to the ErIII mononuclear sandwich complex discussed in Chapter 2. This increase is due to a ferromagnetic dipole-dipole interaction between the ErIII ions through the COT” ring. The aromatic bridging ligand provides a GdIII - GdIII interaction of J = -0.448(1) cm-1. Chapter five extends the discussion of magnetic exchange coupling to include linear K2(THF)4[LnIII2(COT)4] (Ln = Gd, Dy, Er, COT = cyclooctatetraenyl dianion, THF = tetrahydrofuran) complexes of GdIII, DyIII and ErIII. Each complex is composed of two LnCOT2 units bridged linearly by a potassium ion. The magnetic interaction between metal ions is much weaker than in the triple decker complexes discussed in Chapter 4, with a GdIII-GdIII interaction of J = − 0.007(4) cm–1. The magnetic properties of the quadruple decker complexes were compared to their mononuclear equivalents (Chapter 3). Surprisingly, the ErIII complex showed an increase in magnetic blocking temperature over its mononuclear analog despite the large ErIII-ErIII separation of 8.819 Å. Ab initio calculations revealed that this increase is due to single ion effects, most likely an increase in symmetry. Chapter six deviates from lanthanide magnetism to study the magnetic properties of uranium sandwich complexes with multiple ligand systems and oxidation states. Prior to this study the SMM behaviour of uranium sandwich complexes was unknown. We report the synthesis, structure and magnetic properties of both uranium-COT” sandwich complexes and uranium-cycloheptatrienyl complexes with oxidation states spanning (III)-(V). None of the complexes showed zero-field SMM behaviour, indicating a sandwichtype ligand is not appropriate for harnessing the SMM character in uranium. We compared the slow magnetic relaxation of isostructural and valence isoelectronic uranium and neodymium complexes. The improved energy barrier in the uranium complex further motivates the use of uranium in SMM design due to its large spin-orbit coupling.