Increasing the Magnetic Blocking Temperature of Single-Molecule Magnets.

The synthesis of single-molecule magnets (SMMs), magnetic complexes capable of retaining magnetization blocking for a long time at elevated temperatures, has been a major concern for magnetochemists over the last three decades. In this review, we describe basic SMMs and the different approaches that allow high magnetization-blocking temperatures to be reached. We focus on the basic factors affecting magnetization blocking, magnetic axiality and the height of the blocking barrier, which can be used to group different families of complexes in terms of their SMM efficiency. Finally, we discuss several practical routes for the design of mono- and polynuclear complexes that could be applied in memory devices.

A High-Performance Single-Molecule Magnet Utilizing Dianionic Aminoborolide Ligands.

The first example of a homoleptic f-block borolide sandwich complex is presented and shown to be a high-performance single-molecule magnet (SMM). The bis(borolide) complex [K(2.2.2)][[1-(piperidino)-2,3,4,5-tetraphenylborolyl]2Dy] (1) features an unusual example of an anionic Ln3+ metallocene that supports short metal-ligand bonds and a high degree of linearity around the central Dy3+ ion, resulting in comparatively large barriers to magnetization reversal (Ueff = 1600 cm-1 for the most linear orientation) and, importantly, a high blocking temperature (TB, defined as T(τ100s)) of 66 K. These metrics put complex 1 among the very best performing SMMs reported to date and highlight the potential of dianionic borolide ligands to increase ligand field axiality, compared to monoanionic cyclic ligands, to ultimately maximize magnetic anisotropy in f-block-based SMMs.

An intermetallic molecular nanomagnet with the lanthanide coordinated only by transition metals.

Magnetic molecules known as molecular nanomagnets (MNMs) may be the key to ultra-high density data storage. Thus, novel strategies on how to design MNMs are desirable. Here, inspired by the hexagonal structure of the hardest intermetallic magnet SmCo5, we have synthesized a nanomagnetic molecule where the central lanthanide (Ln) ErIII is coordinated solely by three transition metal ions (TM) in a perfectly trigonal planar fashion. This intermetallic molecule [ErIII(ReICp2)3] (ErRe3) starts a family of molecular nanomagnets (MNM) with unsupported Ln-TM bonds and paves the way towards molecular intermetallics with strong direct magnetic exchange interactions-a promising route towards high-performance single-molecule magnets.

Isolation of a triplet benzene dianion.

Baird's rule predicts that molecules with 4n π electrons should be aromatic in the triplet state, but the realization of simple ring systems with such an electronic ground state has been stymied by these molecules' tendency to distort into structures bearing a large singlet-triplet gap. Here, we show that the elusive benzene diradical dianion can be stabilized through creation of a binucleating ligand that enforces a tightly constrained inverse sandwich structure and direct magnetic exchange coupling. Specifically, we report the compounds [K(18-crown-6)(THF)2]2[M2(BzN6-Mes)] (M = Y, Gd; BzN6-Mes = 1,3,5-tris[2',6'-(N-mesityl)dimethanamino-4'-tert-butylphenyl]benzene), which feature a trigonal ligand that binds one trivalent metal ion on each face of a central benzene dianion. Antiferromagnetic exchange in the Gd3+ compound preferentially stabilizes the triplet state such that it becomes the molecular ground state. Single-crystal X-ray diffraction data and nucleus-independent chemical shift calculations support aromaticity, in agreement with Baird's rule.

Substituent Effects on Exchange Coupling and Magnetic Relaxation in 2,2'-Bipyrimidine Radical-Bridged Dilanthanide Complexes.

Systematic analysis of related compounds is crucial to the design of single-molecule magnets with improved properties, yet such studies on multinuclear lanthanide complexes with strong magnetic coupling remain rare. Herein, we present the synthesis and magnetic characterization of the series of radical-bridged dilanthanide complex salts [(Cp*2Ln)2(µ-5,5'-R2bpym)](BPh4) (Ln = Gd, Dy; R = NMe2 (1), OEt (2), Me (3), F (4); bpym = 2,2'-bipyrimidine). Modification of the substituent on the bridging 5,5'-R2bpym radical anion allows the magnetic exchange coupling constant, JGd-rad, for the gadolinium compounds in this series to be tuned over a range from -2.7 cm-1 (1) to -11.1 cm-1 (4), with electron-withdrawing or -donating substituents increasing or decreasing the strength of exchange coupling, respectively. Modulation of the exchange coupling interaction has a significant impact on the magnetic relaxation dynamics of the single-molecule magnets 1-Dy through 4-Dy, where stronger JGd-rad for the corresponding Gd3+ compounds is associated with larger thermal barriers to magnetic relaxation (Ueff), open magnetic hysteresis at higher temperatures, and slower magnetic relaxation rates for through-barrier processes. Further, we derive an empirical linear correlation between the experimental Ueff values for 1-Dy through 4-Dy and the magnitude of JGd-rad for the corresponding gadolinium derivatives that provides insight into the electronic structure of these complexes. This simple model applies to other organic radical-bridged dysprosium complexes in the literature, and it establishes clear design criteria for increasing magnetic operating temperatures in radical-bridged molecules.

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium- and Terbium-[1]Ruthenocenophane Complexes.

We report the first f-block-ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal-prismatic geometry stabilizes the magnetic ground state in the case of Dy3+ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb3+ .

Magnetization Dynamics and Coherent Spin Manipulation of a Propeller Gd(III) Complex with the Smallest Helicene Ligand.

A homoleptic gadolinium(III) complex with the smallest helicene-type ligand, 1,10-phenanthroline-N,N'-dioxide (phendo) [Gd(phendo)4](NO3)3·xMeOH (phendo = 1,10-phenanthroline-N,N'-dioxide, MeOH = methanol), shows slow relaxation of the magnetization characteristic for Single Ion Magnets (SIM), despite negligible magnetic anisotropy, confirmed by ab initio calculations. Solid state dilution magnetic and EPR studies reveal that the magnetization dynamics of the [Gd(phendo)4]3+ cation is controlled mainly by a Raman process. Pulsed EPR experiments demonstrate long phase memory times (up to 2.7 µs at 5 K), enabling the detection of Rabi oscillations at 20 K, which confirms coherent control of its spin state.

Trends in trigonal prismatic Ln-[1]ferrocenophane complexes and discovery of a Ho3+ single-molecule magnet.

Lanthanide metallocenophanes are an intriguing class of organometallic complexes that feature rare six-coordinate trigonal prismatic coordination environments of 4f elements with close intramolecular proximity to transition metal ions. Herein, we present a systematic study of the structural and magnetic properties of the ferrocenophanes, [LnFc3(THF)2Li2]-, of the late trivalent lanthanide ions (Ln = Gd (1), Ho (2), Er (3), Tm (4), Yb (5), Lu (6)). One major structural trend within this class of complexes is the increasing diferrocenyl (Fc2-) average twist angle with decreasing ionic radius (r ion) of the central Ln ion, resulting in the largest average Fc2- twist angles for the Lu3+ compound 6. Such high sensitivity of the twist angle to changes in r ion is unique to the here presented ferrocenophane complexes and likely due to the large trigonal plane separation enforced by the ligand (>3.2 Å). This geometry also allows the non-Kramers ion Ho3+ to exhibit slow magnetic relaxation in the absence of applied dc fields, rendering compound 2 a rare example of a Ho-based single-molecule magnet (SMM) with barriers to magnetization reversal (U) of 110-131 cm-1. In contrast, compounds featuring Ln ions with prolate electron density (3-5) don't show slow magnetization dynamics under the same conditions. The observed trends in magnetic properties of 2-5 are supported by state-of-the-art ab initio calculations. Finally, the magneto-structural relationship of the trigonal prismatic Ho-[1]ferrocenophane motif was further investigated by axial ligand (THF in 2) exchange to yield [HoFc3(THF*)2Li2]- (2-THF*) and [HoFc3(py)2Li2]- (2-py) motifs. We find that larger average Fc2- twist angles (in 2-THF* and 2-py as compared to in 2) result in faster magnetic relaxation times at a given temperature.

Holmium(iii) molecular nanomagnets for optical thermometry exploring the luminescence re-absorption effect.

Coordination complexes of lanthanide(3+) ions can combine Single-Molecule Magnetism (SMM) with thermally modulated luminescence applicable in optical thermometry. We report an innovative approach towards high performance SMM-based optical thermometers which explores tunable anisotropy and the luminescence re-absorption effect of HoIII complexes. Our concept is shown in dinuclear cyanido-bridged molecules, {[HoIII(4-pyridone)4(H2O)2][MIII(CN)6]}·nH2O (M = Co, 1; Rh, 2; Ir, 3) and their magnetically diluted analogues, {[HoIII x YIII 1-x (4-pyridone)4(H2O)2][MIII(CN)6]}·nH2O (M = Co, x = 0.11, 1@Y; Rh, x = 0.12, 2@Y; Ir, x = 0.10, 3@Y). They are built of pentagonal bipyramidal HoIII complexes revealing the zero-dc-field SMM effect. Experimental studies and the ab initio calculations indicate an Orbach magnetic relaxation with energy barriers varying from 89.8 to 86.7 and 78.7 cm-1 K for 1, 2, and 3, respectively. 1-3 also differ in the strength of quantum tunnelling of magnetization which is suppressed by hyperfine interactions, and, further, by the magnetic dilution. The YIII-based dilution governs the optical properties as 1-3 exhibit poor emission due to the dominant re-absorption from HoIII while 1@Y-3@Y show room-temperature blue emission of 4-pyridone. Within ligand emission bands, the sharp re-absorption lines of the HoIII electronic transitions were observed. Their strong thermal variation was used in achieving highly sensitive ratiometric optical thermometers whose good performance ranges, lying between 25 and 205 K, are adjustable by using hexacyanidometallates. This work shows that HoIII complexes are great prerequisites for advanced opto-magnetic systems linking slow magnetic relaxation with unique optical thermometry exploiting a luminescence re-absorption phenomenon.

Effects of the Exchange Coupling on Dynamic Properties in a Series of CoGdCo Complexes.

Reaction of 2-hydroxy3-methoxybenzaldehyde ( o-vanillin) with 1,1,1-tris(aminomethyl)ethane, Me-C(CH2NH2)3, or with N, N', N''-trimethylphosphorothioic trihydrazide, P(S)[NMe-NH2]3, yields two tripodal LH3 and L1H3 ligands which are able to give cationic heterotrinuclear [LCoGdCoL]+ or [L1CoGdCoL1]+ complexes. The CoII ions are coordinated to these deprotonated ligands in the inner N3O3 site, while the GdIII ion is linked to three deprotonated phenoxo oxygen atoms of two anionic [LCo]- or [L1Co]- units. Air oxidation of these trinuclear complexes does not yield complexes associating CoIII and GdIII ions. With the first ligand, the structurally characterized resulting complex is the neutral mononuclear LCoIII compound, while in the second case, oxidation of the CoII ions turned out to be impossible. The [L1CoLnCoL1]+ complexes behave as single-molecule magnets with effective energy barriers for the reversal of magnetization varying from Ueff = 51.3 K, τo = 2 × 10-6 s for the yttrium complex to Ueff = 29.5, 29.4, 27.4 K and τo = 1.3 × 10-7, 1.47 × 10-7, 1.50 × 10-7 s for the gadolinium ones, depending on the used counteranions. The energy decrease is compensated by the suppression of quantum tunneling of magnetization in absence of applied field, thanks to the introduction of a ferromagnetic Co-Gd interaction. Current work also shows that uncritical use of conventional spin Hamiltonians, based on quenched orbital momenta, can be misleading and that ab initio calculations are indispensable for establishing the picture of real magnetic interaction. Ab initio calculations show that the CoII sites in the investigated compounds possess large unquenched orbital moments due to the first-order spin-orbit coupling resulting in strongly axial magnetic anisotropy. Although the CoII ions are not axial enough for showing slow relaxation of magnetization by themselves, blocking barriers of exchange type are obtained thanks to the exchange interaction with GdIII ions.

Magnetization Blocking in Fe2 III Dy2 III Molecular Magnets: Ab Initio Calculations and EPR Spectroscopy.

The magnetism and magnetization blocking of a series of [Fe2 Dy2 (OH)2 (teaH)2 (RC6 H4 COO)6 ] complexes was investigated, in which teaH3 =triethanolamine and R=meta-CN (1), para-CN (2), meta-CH3  (3), para-NO2  (4) and para-CH3  (5), by combining ab initio calculations and EPR measurements. The results of broken-symmetry DFT calculations show that in all compounds the Fe-Fe exchange interaction is antiferromagnetic and stronger by far than the Fe-Dy and Dy-Dy interactions. As a result, the lowest two exchange doublets probed by EPR spectroscopy mostly originate from the Ising interaction of the dysprosium ions in all compounds. A correct quantitative description of the splitting of these two doublets requires, however, an explicit account of the Fe-Dy and Fe-Fe interactions. Due to the inversion symmetry of the complexes, the doublets under consideration are described by a collinear Ising exchange interaction. This picture is also supported by the EPR spectra, which could be simulated with parameters close to those extracted from the calculations. The magneto-structural analysis shows an increase of the antiferromagnetic Fe-Fe exchange interaction with increasing Fe-O-Fe angle and Fe-Fe distance. For the Dy-Fe interaction, the opposite tendency is observed, that is, a decrease of antiferromagnetic exchange coupling with increasing Dy-O-Fe angle and Dy-Fe distance. The transversal g factors extracted from the ab initio calculations have values in the range of 0.01-0.2, testifying to the lack of high axiality of the ground state of the dysprosium ions. This explains the lack/poor single-molecule magnetic behavior of this series of compounds at the investigated temperatures of a few Kelvin. Due to a very small gap (fractions of a wavenumber) between the ground and first-excited exchange doublet, relaxation takes place by magnetic moment reversal at individual dysprosium sites in the considered temperature domain.

Magnetic Properties of a Terbium-[1]Ferrocenophane Complex: Analogies between Lanthanide-Ferrocenophane and Lanthanide-Bis-phthalocyanine Complexes.

A rare example of an organometallic terbium single-ion magnet is reported. A Tb3+ -[1]ferrocenophane complex displays a larger barrier to magnetization reversal than its isostructural Dy3+ analogue, which is reminiscent of trends observed for lanthanide-bis-phthalocyanine complexes. Detailed ab initio calculations support the experimental observations and suggest a significantly larger ground-state stabilization for the non-Kramers ion Tb3+ in the Tb complex than for the Kramers-ion Dy3+ in the Dy complex.

Coupling Influences SMM Properties for Pure 4 f Systems.

Increasing both the energy barrier for magnetization reversal and the coercive field of the hysteresis loop are significant challenges in the field of single-molecule magnets (SMMs). Coordination geometries of lanthanide ions and magnetic interactions between lanthanide ions are both important for guiding the magnetic behavior of SMMs. We report a high energy barrier of 657 K (457 cm-1 ) in a diamagnetic-ion-diluted lanthanide chain compound with a constrained bisphenoid symmetry (D2d ); this energy barrier is substantially higher than the barrier of 567 K (394 cm-1 ) of the non-diluted chain compound with intrachain ferromagnetic interactions. Although intrachain magnetic interaction lowers the energy barrier for magnetization reversal, it can greatly enhance the coercive fields and zero-field remanence of the hysteresis loops, which is crucial for the rational design of high-performance SMMs. Factors related to the coordination sphere of the lanthanide center, which govern the high magnetic relaxation barriers through the second excited Kramer's doublets and the magnetic interactions that affect the hysteresis loops, were revealed through ab initio calculations.

Transitions of two magnetic interaction states in dinuclear Dy(iii) complexes via subtle structural variations.

Herein we explored the transitions of two magnetic interaction states (antiferromagnetic or ferromagnetic) upon structural variations in two dinuclear Dy(iii) complexes.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of NiII-LnIII-WV trimetallics, [(CN)7W(CN)Ni(H2O)(valpn)Ln(H2O)4]·H2O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic DyIII and TbIII metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [WVNiIILnIII] core structure, [(CN)7W(CN)Ni(dmf)(valdmpn)Ln(dmf)4]·H2O (Ln = GdIII 7, TbIII 8a, DyIII 9, HoIII 10), [(CN)7W(CN)Ni(H2O)(valdmpn)Tb(dmf)2.5(H2O)1.5]·H2O·0.5dmf 8b, and [(CN)7W(CN)Ni(H2O)(valdmpn)Er(dmf)3(H2O)1]·H2O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel site, precluding magnetization blocking in complexes with fewer axial Ln ions. Further analysis has shown that, in the absence of ZFS on Ni ion, all compounds in the two series (except those containing Y and Gd) would be SMMs. The same situation arises for perfectly axial ZFS on Ni(II) with the main anisotropy axis parallel to the main magnetic axis of Ln(III) ions. In all other cases the ZFS on Ni(II) will worsen the SMM properties. The general conclusion is that the design of efficient SMMs on the basis of such complexes should involve isotropic or weekly anisotropic metal ions, such as Mn(II), Fe(III), etc., along with strongly axial lanthanides.

Magnetic frustration in a hexaazatrinaphthylene-bridged trimetallic dysprosium single-molecule magnet.

The synthesis, structure and magnetic properties of the HAN-bridged tri-dysprosium complex [{(thd)3Dy}3HAN] (1) are described. The complex is an SMM that shows two relaxation processes owing to the presence of two geometrically distinct Dy3+ sites in 1. Ab initio calculations reveal that the magnetic ground state of 1 is characterized by magnetic frustration.

A Stable Pentagonal Bipyramidal Dy(III) Single-Ion Magnet with a Record Magnetization Reversal Barrier over 1000 K.

Single-molecule magnets (SMMs) with a large spin reversal barrier have been recognized to exhibit slow magnetic relaxation that can lead to a magnetic hysteresis loop. Synthesis of highly stable SMMs with both large energy barriers and significantly slow relaxation times is challenging. Here, we report two highly stable and neutral Dy(III) classical coordination compounds with pentagonal bipyramidal local geometry that exhibit SMM behavior. Weak intermolecular interactions in the undiluted single crystals are first observed for mononuclear lanthanide SMMs by micro-SQUID measurements. The investigation of magnetic relaxation reveals the thermally activated quantum tunneling of magnetization through the third excited Kramers doublet, owing to the increased axial magnetic anisotropy and weaker transverse magnetic anisotropy. As a result, pronounced magnetic hysteresis loops up to 14 K are observed, and the effective energy barrier (Ueff = 1025 K) for relaxation of magnetization reached a breakthrough among the SMMs.

Giant exchange interaction in mixed lanthanides.

Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction.

Redox Switches for Single-Molecule Magnet Activity: An Ab Initio Insight.

A dinuclear Co(II) complex (1) featuring unprecedented anodic and cathodic switches for single-molecule magnet (SMM) activity has been recently investigated (J. Am. Chem. Soc. 2013, 135, 14670). The presence of sandwiched radicals in different oxidation states of this compound mediates magnetic coupling between the high-spin (S=3/2) cobalt ions, which gives rise to SMM activity in both the oxidized ([1(OEt2)](+)) and reduced ([1](-)) states. This feature represents the first example of a SMM exhibiting fully reversible, dual ON/OFF switchability. Here we apply ab initio and broken-symmetry DFT calculations to elucidate the mechanisms responsible for magnetic properties and magnetization blocking in these compounds. It is found that due to the strong delocalization of the magnetic molecular orbital, there is a strong antiferromagnetic interaction between the radical and cobalt ions. The lack of high axiality of the cobalt centres explains why these compounds possess slow relaxation of magnetization only in an applied dc magnetic field.

Magneto-structural correlations in arsenic- and selenium-ligated dysprosium single-molecule magnets.

The structures and magnetic properties of the arsenic- and selenium-ligated dysprosium single-molecule magnets (SMMs) [Cp'3Dy(AsH2Mes)] (3-Dy), [(η5-Cp'2Dy){µ-As(H)Mes}]3 (4-Dy), [Li(thf)4]2[(η5-Cp'2Dy)3(µ3-AsMes)3Li] ([Li(thf)4]2[5-Dy]), and [(η5-Cp'2Dy){µ-SeMes}]3 (6-Dy) are described. The arsenic-ligated complexes 4-Dy and 5-Dy are the first SMMs to feature ligands with metalloid elements as the donor atoms. The arsenide-ligated complex 4-Dy and the selenolate-ligated complex 6-Dy show large anisotropy barriers in the region of 250 cm-1 in zero d.c. field, increasing to 300 cm-1 upon 5% magnetic dilution. Theoretical studies reveal that thermal relaxation in these SMMs occurs via the second-excited Kramers' doublet. In contrast, the arsinidene-ligated SMM 5-Dy gives a much smaller barrier of 23 cm-1, increasing to 35 cm-1 upon dilution. The field-dependence of the magnetization for 4-Dy and 5-Dy at 1.8 K show unusual plateaus around 10 kOe, which is due to the dominance of arsenic-mediated exchange over the dipolar exchange. The effects of the exchange interactions are more pronounced in 5-Dy, which is a consequence of a small but significant increase in the covalent contribution to the predominantly ionic dysprosium-arsenic bonds. Whereas the magnetically non-dilute dysprosium SMMs show only very narrow magnetization versus field hysteresis loops at 1.8 K, the impact of magnetic dilution is dramatic, with butterfly-shaped loops being observed up to 5.4 K in the case of 4-Dy. Our findings suggest that ligands with heavier p-block element donor atoms have considerable potential to be developed more widely for applications in molecular magnetism.