Lanthanides have been investigated extensively for potential applications in quantum information processing and high-density data storage at the molecular and atomic scale. Experimental achievements include reading and manipulating single nuclear spins, exploiting atomic clock transitions for robust qubits and, most recently, magnetic data storage in single atoms. Single-molecule magnets exhibit magnetic hysteresis of molecular origin-a magnetic memory effect and a prerequisite of data storage-and so far lanthanide examples have exhibited this phenomenon at the highest temperatures. However, in the nearly 25 years since the discovery of single-molecule magnets, hysteresis temperatures have increased from 4 kelvin to only about 14 kelvin using a consistent magnetic field sweep rate of about 20 oersted per second, although higher temperatures have been achieved by using very fast sweep rates (for example, 30 kelvin with 200 oersted per second). Here we report a hexa-tert-butyldysprosocenium complex-[Dy(Cp)][B(CF)], with Cp = {CHBu-1,2,4} and Bu = C(CH)-which exhibits magnetic hysteresis at temperatures of up to 60 kelvin at a sweep rate of 22 oersted per second. We observe a clear change in the relaxation dynamics at this temperature, which persists in magnetically diluted samples, suggesting that the origin of the hysteresis is the localized metal-ligand vibrational modes that are unique to dysprosocenium. Ab initio calculations of spin dynamics demonstrate that magnetic relaxation at high temperatures is due to local molecular vibrations. These results indicate that, with judicious molecular design, magnetic data storage in single molecules at temperatures above liquid nitrogen should be possible.

We report the first near-linear bis(amide) 4f-block compound and show that this novel structure, if implemented with dysprosium(III), would have unprecedented single molecule magnet (SMM) properties with an energy barrier, Ueff, for reorientation of magnetization of 1800 cm(-1).

The origin of 60 K magnetic hysteresis in the dysprosocenium complex [Dy(Cp)][B(CF)] (Cp = CHBu-1,2,4, 1-Dy) remains mysterious, thus we envisaged that analysis of a series of [Ln(Cp)] (Ln = lanthanide) cations could shed light on these properties. Herein we report the synthesis and physical characterization of a family of isolated [Ln(Cp)] cations (1-Ln; Ln = Gd, Ho, Er, Tm, Yb, Lu), synthesized by halide abstraction of [Ln(Cp)(Cl)] (2-Ln; Ln = Gd, Ho, Er, Tm, Yb, Lu). Complexes within the two families 1-Ln and 2-Ln are isostructural and display pseudo-linear and pseudo-trigonal crystal fields, respectively. This results in archetypal electronic structures, determined with CASSCF-SO calculations and confirmed with SQUID magnetometry and EPR spectroscopy, showing easy-axis or easy-plane magnetic anisotropy depending on the choice of Ln ion. Study of their magnetic relaxation dynamics reveals that 1-Ho also exhibits an anomalously low Raman exponent similar to 1-Dy, both being distinct from the larger and more regular Raman exponents for 2-Dy, 2-Er, and 2-Yb. This suggests that low Raman exponents arise from the unique spin-phonon coupling of isolated [Ln(Cp)] cations. Crucially, this highlights a direct connection between ligand coordination modes and spin-phonon coupling, and therefore we propose that the exclusive presence of multihapto ligands in 1-Dy is the origin of its remarkable magnetic properties. Controlling the spin-phonon coupling through ligand design thus appears vital for realizing the next generation of high-temperature single-molecule magnets.

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The proposal that paramagnetic transition metal complexes could be used as qubits for quantum information processing (QIP) requires that the molecules retain the spin information for a sufficient length of time to allow computation and error correction. Therefore, understanding how the electron spin-lattice relaxation time ( T 1 ) and phase memory time ( T m ) relate to structure is important. Previous studies have focused on the ligand shell surrounding the paramagnetic centre, seeking to increase rigidity or remove elements with nuclear spins or both. Here we have studied a family of early 3d or 4f metals in the +2 oxidation states where the ground state is effectively a 2 S state. This leads to a highly isotropic spin and hence makes the putative qubit insensitive to its environment. We have studied how this influences T 1 and T m and show unusually long relaxation times given that the ligand shell is rich in nuclear spins and non-rigid.

We report the synthesis and characterization of the uranium(III) triamide complex [UIII(N**)3] [1, N**=N(SiMe2tBu)2−]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three-coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N“)3] (N”=N(SiMe3)2−), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N“)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single-molecule magnets.

We report a study of quantum tunneling of the magnetisation in three Dy(iii) single-molecule magnets.

Following our report of the first near-linear lanthanide (Ln) complex, [Sm(N)] (1), herein we present the synthesis of [Ln(N)] [N = {N(SiPr)}; Ln = Eu (2), Tm (3), Yb (4)], thus achieving approximate uniaxial geometries for a series of "traditional" Ln ions. Experimental evidence, together with calculations performed on a model of 4, indicates that dispersion forces are important for stabilization of the near-linear geometries of 1-4. The isolation of 3 under a dinitrogen atmosphere is noteworthy, given that "[Tm(N″)(μ-N″)]" (N″ = {N(SiMe)}) has not previously been structurally authenticated and reacts rapidly with N(g) to give [{Tm(N″)}(μ-η:η-N)]. Complexes 1-4 have been characterized as appropriate by single-crystal X-ray diffraction, magnetic measurements, electrochemistry, multinuclear NMR, electron paramagnetic resonance (EPR), and electronic spectroscopy, along with computational methods for 3 and 4. The remarkable geometries of monomeric 1-4 lead to interesting physical properties, which complement and contrast with comparatively well understood dimeric [Ln(N″)(μ-N″)] complexes. EPR spectroscopy of 3 shows that the near-linear geometry stabilizes m states with oblate spheroid electron density distributions, validating our previous suggestions. Cyclic voltammetry experiments carried out on 1-4 did not yield Ln reduction potentials, so a reactivity study of 1 was performed with selected substrates in order to benchmark the Sm → Sm couple. The separate reactions of 1 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), azobenzene, and benzophenone gave crystals of [Sm(N)(TEMPO)] (5), [Sm(N)(NPh)] (6), and [Sm(N){μ-OPhC(CH)CPhO-κO,O'}] (7), respectively. The isolation of 5-7 shows that the Sm center in 1 is still accessible despite having two bulky N moieties and that the N-donor atoms are able to deviate further from linearity or ligand scrambling occurs in order to accommodate another ligand in the Sm coordination spheres of the products.