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![Measuring the Spin-Lattice Relaxation Magnetic Field Dependence of Hyperpolarized [1-13C]pyruvate](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59399.jpg&w=3840&q=50)
Measuring the Spin-Lattice Relaxation Magnetic Field Dependence of Hyperpolarized [1-13C]pyruvate
Published on: September 13, 2019
Trinuclear rare earth pyridyl-β-diketonate complexes: developing new methods towards finding lost toroidal spin
Patrick Mangundu1, Kate E Tanner1, Andrew Bloomfield2
1School of Natural Sciences - Chemistry, University of Tasmania, Hobart, Tasmania, Australia. rebecca.fuller@utas.edu.au.
None:
A series of rare earth (RE) 'triangles' have been synthesised to investigate the low energy excitations of toroic molecules using inelastic neutron scattering (INS) experiments. β-Diketonate, 1-(2-pyridinyl)-1,3-butandione (o-pbdH) has been employed to synthesise [{Ho3(O)2(o-pbd)3Cl(H2O)5}2]·8Cl·3H2O·0.5EtOH (1) and [{Dy3(O)2(o-pbd)3Cl(H2O)5}2]·6Cl·2EtOH·2hexane (2). With further examples, [Ho3(OH)2(o-pbd)3Cl(H2O)3(EtOH)2]·3Cl (3), [{Ho3(OH)2(o-pbd)3Cl(H2O)5}2]·6Cl·2H2O (4) and [Dy3(O)(OH)(o-pbd)3(NO3)4(H2O)2]·2NO3·H2O (5) aimed towards the generation of variation in coordinated ancillary ligands that are capable of reducing symmetry and inhibiting toroic behaviour. A sterically bulky 3-(1-naphthyl)-1-(2-pyridyl)-propane-1,3-dione (o-nppdH) ligand impeded the formation of the RE3 motif with [Dy2(O)2(o-nppd)5(H2O)]·6Cl (6) isolated. The RE3 complexes are structurally similar to known trinuclear based single molecular toroics (SMTs), including RE-β-diketonate analogues prone to mixing between electronic states. Consistent with these, a non-magnetic SMT ground state was not observable in the new complexes utilising conventional magnetometry. Spectroscopic confirmation of toroic properties with INS was attempted for the first time on 1 and the structurally similar SMT [Ho3(OH)2(o-dppd-d10)3Cl(H2O)5]. The observed intensity of a broad Lorentzian at 0.69(1) meV for [Ho3(OH)2(o-dppd)3Cl(H2O)5] and 0.44(1) meV for 1, is remarkably close to the calculated energy gap ∼5 cm-1 (or 0.62 meV) and potentially provides a new probe that can validate complexes with a poorly separated toroidic ground state.
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