Single-molecule Magnet Properties Research Articles

Magnetization Slow Dynamics in Ferrocenium Complexes.

The single-molecule magnet (SMM) properties of a series of ferrocenium complexes, [Fe(η5 -C5 R5 )2 ]+ (R=Me, Bn), are reported. In the presence of an applied dc field, the slow dynamics of the magnetization in [Fe(η5 -C5 Me5 )2 ]BArF are revealed. Multireference quantum mechanical calculations show a large energy difference between the ground and first excited states, excluding the commonly invoked, thermally activated (Orbach-like) mechanism of relaxation. In contrast, a detailed analysis of the relaxation time highlights that both direct and Raman processes are responsible for the SMM properties. Similarly, the bulky ferrocenium complexes, [Fe(η5 -C5 Bn5 )2 ]BF4 and [Fe(η5 -C5 Bn5 )2 ]PF6 , also exhibit magnetization slow dynamics, however an additional relaxation process is clearly detected for these analogous systems.

First step in preparation of multifunctional spin crossover material based on Fe(II) complex of cyclam-based ligand. Magnetism and DFT studies

With the aim to make the first step in preparation of magnetic multifunctional material combining spin crossover (SCO) together with single-molecule magnet (SMM) properties in one molecule (polynuclear complex), a specially designed ligand L-NH2 (1,8-bis(4-aminobenzyl)-4,11-bis(pyridin-2-ylmethyl)-1,4,8,11-tetraazacyclotetradecane) was synthesized. It contains (i) macrocyclic cyclam core substituted with two 2-pyridylmethyl pendant arms suitable for complexation of Fe(II), because such system was previously proven to provide SCO, and (ii) two p-aminobenzyl pendant arms introducing NH2 groups suitable for consequent attachment of SMM molecule (e.g. transformation to functional groups for selective complexation of other metals). Furthermore, Fe(II) complex [Fe(L-NH2)]Cl2·2.5H2O was prepared and characterized. Unfortunately, according to the magnetic measurements, SCO behavior was not observed and the complex remained in high-spin state with relatively high magnetic anisotropy (D = –17.7 cm−1, E/D = 0.31). This magnetic behavior was rationalized by the DFT computational study, which identified high-spin state as preferential for prepared complex in contrast to other structurally similar SCO systems with low-spin state preference. The most probable reason behind this difference appeared to be the electron-withdrawing effect of benzyl groups providing weaker ligand field of macrocyclic nitrogen donor atoms.

A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Devices.

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2′-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5–398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

Spin properties of single-molecule magnet of double-decker Tb(III)-phthalocyanine (TbPc2) on ferromagnetic Co film characterized by spin polarized STM (SP-STM)

We demonstrate a direct visualization of the magnetic hysteresis of a single-molecule magnet bis(phthalocyaninato)terbium(III) (TbPc2) adsorbed on the Co islands, which covers a submonolayer region of an Au(111) surface by utilizing the spin-polarized scanning tunneling microscope (SP-STM) and monitoring the magnetotunneling resistance. We found that the TbPc2 molecule is spin polarized and attached to the ferromagnetic Co islands. The result of the SP-STM measurements showed that the spin of TbPc2 is antiferromagnetically coupled to the magnetization of the Co island. In addition, we found an opening in the hysteresis curve even with the frozen magnetization of the Co island, unlike that with near-zero remanence typically reported for the bulk crystal and the nonmagnetic substrate.

(Invited) New Advances in Magnetic Properties of Endohedral Metallofullerenes

An ongoing quest for lanthanide single molecule magnets (SMMs) operating at ever higher temperatures resulted in an impressive progress over the last two decades. On the next step from fundamental research to prospective applications, i.e. as components of spintronic devices, one has to consider stability and processability of SMM materials. Air-stability, thermal stability, ability to form thin molecular layers on different substrates are among the critical issues to be addressed. Encapsulation of magnetic species within robust molecular containers appears to be a natural route towards SMMs fulfilling required stability criteria. Chemical and thermal stability of carbon cages, fullerenes, makes them perfectly suitable for this goal. Fullerenes can encapsulate up to four metal atoms within their inner space, and a number of lanthanide EMFs was found to show SMM behavior. Besides, EMF-SMMs can form monolayers by sublimation or by self-assembly from solution, and such monolayers retain their SMM properties on metallic substrates. In this contribution we will highlight recent developments in the field of lanthanide-EMFs with peculiar magnetic properties.

Influence of Magnetic Interactions and Single-Ion Anisotropy on Magnetic Relaxation within a Family of Tetranuclear Dysprosium Complexes.

Six tetranuclear DyIII complexes [Dy4(L)2(CH3OH)3(NO3)3]·3NO3·2H2O (1a), [Dy4(L)2(CH3OH)2(SCN)4(OCH3)2]·2CH3OH·2H2O (1b), {[Dy4(L)2(CH3OH)(SCN)6(CH3CN)]·3CH3OH·4CH3CN}2 (2a), [Dy4(L)2(CH3OH)2(SCN)6]·6CH3OH·2H2O (2b), [Dy4(L)2(CH3OH)2(SCN)4(OCH3)2]·5CH3OH·2H2O (3a), and [Dy4(L)2(CH3OH)(SCN)5(H2O)2]·SCN·4CH3OH·2H2O (3b) were structurally and magnetically characterized. The Dy1/Dy2 centers in these complexes are eight-coordinate and submitted to pseudo- D4d symmetry environments. It is noteworthy that the modulation of coordination terminal around Dy1/Dy2 centers induces distinct magnetic relaxation processes, switching from single relaxation (1b) to two-step relaxation (2b). All complexes show significant zero-field single-molecule magnet (SMM) properties with the exception of 3b, which only features the slow magnetic relaxation behavior under a zero dc field. Ab initio calculations substantiate that the excellent SMM property of complex 1b should mainly profit from strong ferromagnetic interactions between the individual DyIII ions, while different single-ion magnetism results in better SMM property of complex 3a than that of 3b.

Synthesis, structures and magnetic properties of cyano- and amide-bridged FeIII-LnIII tetranuclear heterometallic clusters

Three FeIII2LnIII2 tetranuclear heterometallic clusters, [H4LGd(H2O)Tp*Fe(CN)3]2·8H2O·2MeOH (1) and [H4LLn(MeOH)Tp*Fe(CN)3]2·6MeOH·2MeCN (Ln = Tb and Dy for 2 and 3, respectively, H6L = N,N′-(2,6-pyridine-dicarboxyl)-disalicylhydrazide, Tp* = hydridotris(3,5dimethylpyrazol-1-yl)-borate), were synthesized by use of the [(Tp*)Fe(CN)3]− unit as a metalloligand toward LnCl3 and H6L species. Structural analyses reveal that FeIII and LnIII ions in all complexes are connected to each other by one cyanide to form a heterobinuclear unit of [Ln(H4L)][(Tp*)Fe(CN)3], which is dimerized through Ln–N–C = O–Ln interaction. Magnetic susceptibility measurements show weak antiferromagnetic interactions between cyano-bridged FeIII and GdIII ions and amide-bridged GdIII ions are operative. Complex 1 displays the magnetocaloric effect with −ΔSmmax = 12.70 J·kg−1·K−1 at 4.0 K for ΔH = 7 T. No single-molecule magnetic properties are observed for 2 or 3 down to 1.8 K.

Synthesis, Structures, and Single-Molecule Magnetic Properties of Three Dy2 Complexes.

To explore the influences of the subtle structural variations in the ligand backbones on the single-molecule magnetic properties of dinuclear dysprosium(III) complexes, three ligands-H2 L1 (H2 L1 =N1 ,N3 -bis(salicylaldehyde)diethylenetriamine), H2 L2 (H2 L2 =N1 ,N3 -bis(3-methoxysalicylidene)diethylenetriamine), and H2 L3 (H2 L3 =N1 ,N3 -bis(5-chlorosalicyladehyde)diethylenetriamine)-were synthesized and employed to prepare the expected dinuclear dysprosium(III) complexes. The three ligands differ in terms of the substituents at the benzene rings of the salicylaldehyde moieties. The reactions of Dy(NO3 )3 ⋅6 H2 O, pivalic acid, and the ligands H2 L1 , H2 L2 , and H2 L3 generated complexes with the formulae [Dy2 (L1 )2 (piv)2 ] (1), [Dy2 (L2 )2 (piv)2 ] (2), and [Dy2 (L3 )2 (piv)2 ]⋅ 2 MeCN (3), respectively. The purposeful attachment of the functional groups with varied sizes at the benzene rings of the salicylaldehyde backbones resulted in slight differences in the Dy-O-Dy bond angles and the Dy⋅⋅⋅Dy bond lengths in 1-3; consequently, the three complexes exhibited distinct magnetic properties. They all showed slow magnetization relaxation with energy barriers of 40.32 (1), 31.67 (2), and 33.53 K (3). Complete active space self-consistent field (CASSCF) calculations were performed on complexes 1-3 to rationalize the slight discrepancy observed in the magnetic behavior. The calculated results satisfactorily explained the experimental outcomes.

Inelastic Neutron Scattering of Lanthanoid Complexes and Single‐Molecule Magnets

Single‐molecule magnets (SMMs) are discrete metal complexes that retain their magnetisation below a certain temperature, with possible applications in quantum information processing, molecular spintronics and high‐density data storage. Complexes of lanthanoid(III) ions have proven highly successful in the field, some exhibiting magnetic hysteresis at liquid nitrogen temperatures. Inelastic neutron scattering (INS), widely used for the study of the crystal field splitting engendered by the coordination environment of metal centres, can afford a wealth of information when applied to the study of these molecular nanomagnets, as the SMM properties arise from the electronic structure of the lanthanoid(III) ions. Although relatively underutilised to date, INS can be employed alongside crystal field analysis, and/or ab initio calculations, to understand how subtle structural changes impact SMM behaviour. In this Minireview we discuss the application of INS to the study of lanthanoid complexes, to elucidate both crystal field splitting and exchange coupling in coupled metal‐radical and metal‐metal SMMs.

Detailed Analysis of the Crystal Structures and Magnetic Properties of a Dysprosium(III) Phthalocyaninato Sextuple-Decker Complex: Weak f-f Interactions Suppress Magnetic Relaxation.

In the research field of single-molecule magnets (SMMs), lanthanoid-lanthanoid interactions, so-called f-f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f-f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII -CdII -phthalocyaninato sextuple-decker complex (Dy2 Cd3 ) reveals that the intramolecular Dy-Dy length in Dy2 Cd3 is more than 13 Å, which is longer than the intermolecular Dy-Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole-dipole interactions are observed in Dy2 Cd3 . From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2 Cd3 is partially suppressed owing to the existence of very weak Dy-Dy interactions. Our results show that even very weak Dy-Dy interactions act as a dipolar bias, suppressing QTM.

Twists to the Spin Structure of the Ln9-diabolo Motif Exemplified in Two {Zn2Ln2}[Ln9]{Zn2} Coordination Clusters.

Two pentadecanuclear Zn4Ln11 [with Ln = Gd(1) or Dy(2)] coordination clusters, best formulated as {Zn2Ln2}[Ln9]{Zn2}, are presented. The central {Ln9} diabolo core has a {Zn2Ln2} handle motif pulling at two outer Ln ions of the central core via two {ZnLn} units, which also invest the system with C2 point symmetry. The resulting cluster motif is supported on two Zn "feet", corresponding to the {Zn2} unit in the formula. A thorough investigation of the magnetic properties in the light of the properties of previously reported {Ln9} diabolo compounds was undertaken. Up to now, the spin structure of such diabolo motifs usually proves ambiguous. Our magnetic studies show that the orientation of the central spin in the {Gd9} diabolo plays a decisive role. In stabilizing the core by attachment of the {Zn}2+ "feet" and using the C2 symmetry related {ZnGd}5+ handles to influence the spin direction of the central Gd of the {Gd9} diabolo, we can understand why the "naked" {Gd9} diabolo shows ambiguous spin structure. This then allowed us to elucidate the single-molecule magnetic (SMM) properties of the Dy-based compound 2 through disentangling the magnetic properties of the isostructural Gd-based compound 1.

Recent advances in single molecule magnetism of dysprosium-metallofullerenes.

This article outlines the magnetic properties of single molecule magnets based on Dy-encapsulating endohedral metallofullerenes. The factors that govern these properties, such as the influence of different non-metal species in clusterfullerenes, the cage size, and cage isomerism are discussed, as well as the recent successful isolation of dimetallofullerenes with unprecedented magnetic properties. Finally, recent advances towards the organization of endohedral metallofullerenes in 1D, 2D, and 3D ordered structures with potential for devices are reviewed.

Quantum tunnelling of the magnetisation in single-molecule magnet isotopologue dimers.

Quantum tunnelling of the magnetisation plays a major role in the magnetic properties of lanthanide Single-Molecule Magnets: while it is considered a problem for data storage device applications since it leads to information loss, it is an essential pre-requisite for the read-out and manipulation of the nuclear states in Quantum Information Processing schemes. Here we describe two isotopologue dysprosium dimers, i.e. [(163Dy(tmhd)3)2(bpym)] and [(164Dy(tmhd)3)2(bpym)] (tmd = tris(tetramethylheptanedionato) and bpym = bipyrimidine), where the nuclear spin presence or absence clearly affects the magnetic properties of the systems. Through μ-SQUID studies at milli-Kelvin temperatures and alternating current magnetic measurements, we find significant differences in the magnetic behaviour of both complexes. While simulation of the hysteresis loops at 30 mK reveals that the presence of nuclear spin does not influence the tunnelling rate, we find that it facilitates the coupling to the phonon bath enhancing the direct relaxation process; an observation reflected in the temperature and field dependence of the relaxation rates.

Linear hexanuclear helical dysprosium single-molecule magnets: the effect of axial substitution on magnetic interactions and relaxation dynamics.

The reaction between the rigid Schiff-base ligand H4L ([3,6-bis(2-hydroxy-3-methoxybenzylidene)hydrazinecarbonyl]-pyridazine) and different dysprosium(iii) salts afforded two new linear hexanuclear helical clusters, [Dy6L3(SCN)6(DMF)8]·4DMF (1), and [Dy6L3(NO3)6(DMF)4(H2O)2]·8DMF (2), which possess a similar Dy6 core with [Dy6L3(PhCOO)6(CH3OH)6]·11CH3OH·H2O (3). Modulation of the axial ligands around DyIII sites causes different coordination geometries and magnetic interactions, resulting in distinct magnetic relaxation behaviors. Compounds 1 and 2 show typical single-molecule magnet (SMM) properties with effective barriers (Ueff) of 15 and 68 K, respectively, which could greatly profit from strong ferromagnetic interactions compared with compound 3. Presence of a hula-hoop-like geometry of the DyIII ions and stronger ferromagnetic interactions results in better SMM performance of compound 2 than that of 1.

The effect of the second coordination sphere on the magnetism of [Ln(NO3)3(H2O)3]·(18-crown-6) (Ln = Dy and Er).

The objective of this work was the exploration of the effect of the second coordination sphere on the magnetic properties of [Ln(NO3)3(H2O)3]·(18C6) (Ln = Dy (1) and Er (2)) compounds comprising co-crystallized 18-crown-6 ethers. Both compounds were identified as field-induced single molecule magnets (SMMs) with estimated magnetization reversal barriers Ueff = 66–71 K for 1 and Ueff = 21–24 K for 2. Theoretical calculations with the B3LYP functional revealed substantial change and redistribution of the electrostatic potential upon accounting for the second coordination sphere represented by two 18C6 molecules, which resulted in the change of the crystal-field around metal atoms. As a result, the multireference CASSCF calculations exposed significant impact of the second coordination sphere on the energy splitting of the respective 6H15/2 (DyIII) and 4I15/2 (ErIII) ground states, the magnetization reversal barrier and the magnetic anisotropy parameters. Moreover, the calculated magnetization reversal barriers, Ucalc. = 57 K for 1 and Ucalc. = 16 K for 2, are in good agreement with the experimental values accentuating the importance of the second coordination sphere on the magnetic properties of SMMs.

Neodymium β-diketonate showing slow magnetic relaxation and acting as a ratiometric thermometer based on near-infrared emission

Self-assembly of β-diketonate (Htta = thenoyl(trifluoro)acetone) and 4,4′-azopyridine (Azo-py) with neodymium(iii) ions in the presence of methanol resulted in the formation of mononuclear complex [NdIII(TTA)3(MeOH)2]·0.5Azo-py (A) in which two asymmetric units are linked by Azo-py through hydrogen bonding via methanol. A reveals near-infrared emission (NIR) centred at about 895 and 1056 nm, in the 10–370 K temperature range, originating from the two emissive transitions on Nd(iii) from 4F3/2 to 4I9/2 and 4I11/2 levels, respectively. Furthermore, the NIR luminescence intensity of A at room temperature augments two times upon thermal elimination of one coordinated methanol molecule. The thermally activated A exhibits single centre ratiometric thermometer behaviour in a wide temperature range from 10 to 300 K. Moreover, fluorescence properties of A were compared to another mononuclear complex [NdIII(TTA)3(4-OHpy)(H2O)] (B). Assembly A also exhibits field-induced slow magnetic relaxation properties with an energy barrier of ΔE/kB = 19.7(7) K and an attempt time of relaxation, τ0 = 3.7(8) × 10−7 s for fresh sample A, and ΔE/kB = 27.3 K and τ0 = 8.5(0) × 10−8 for assembly A after thermal treatment at 370 K.

Studies of Er(iii)–W(v) compounds showing nonlinear optical activity and single-molecule magnetic properties

Studies of {[Er(dma)5][W(CN)8]}n (1) showing nonlinear optical effect of second harmonic generation, and [Er(dma)5(H2O)2]·[W(CN)8]·dma·H2O (2) and [Er(dma)4(H2O)3]·[W(CN)8]·dma·3H2O (3) revealing field-induced single molecule magnet behavior.

Organic chelate-free and azido-rich metal clusters and coordination polymers from the use of Me3SiN3: a new synthetic route to complexes with beautiful structures and diverse magnetic properties.

In this Feature Article, we highlight the feasibility of a new, recently developed approach towards the synthesis of high-spin molecules and single-molecule magnets (SMMs). The key to the preparation of such molecular compounds is the organic azide precursor Me3SiN3, which fosters the formation of 3d-metal azido clusters and coordination polymers without requiring the assistance of any organic chelating/bridging group. All the isolated compounds contain metallic cores which are surrounded by end-on bridging N3- groups. Consequently, the reported molecular materials exhibit ferromagnetic exchange interactions between the spin carriers, resulting in the stabilization of the maximum possible spin ground states. The additional presence of magnetic anisotropy, depending on the 3d-metal ion used, gives rise to SMM properties with interesting and rare features. This article intends to introduce the readers to an unexplored, but in coordination chemistry very useful azido-based reagent and emphasize the pronounced differences in the structures and magnetic properties of the compounds that result from the reactions between 3d-metals and NaN3 or Me3SiN3 in the presence of organic bridging groups, and 3d-metals with Me3SiN3 alone.

Mechanism of magnetisation relaxation in {MIII2DyIII2} (M = Cr, Mn, Fe, Al) "Butterfly" complexes: how important are the transition metal ions here?

We describe the synthesis, characterisation and magnetic studies of four tetranuclear, isostructural "butterfly" heterometallic complexes: [MIII2LnIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (H2L = 2,2'-((pyridin-2-ylmethyl)azanediyl)bis(ethan-1-ol), M = Cr, Ln = Dy (1), Y (2), M = Mn, Ln = Dy (3), Y (4)), which extend our previous study on the analogous 5 {Fe2Dy2}, 6 {Fe2Y2} and 7 {Al2Dy2} compounds. We also present data on the yttrium diluted 7 {Al2Dy2}: 8 {Al2Dy0.18Y1.82}. Compounds dc and ac magnetic susceptibility data reveal single-molecule magnet (SMM) behaviour for complex 3 {Mn2Dy2}, in the absence of an external magnetic field, with an anisotropy barrier U eff of 19.2 K, while complex 1 {Cr2Dy2}, shows no ac signals even under applied dc field, indicating absence of SMM behaviour. The diluted sample 8 {Al2Dy0.18Y1.82} shows field induced SMM behaviour with an anisotropy barrier U eff of 69.3 K. Furthermore, the theoretical magnetic properties of [MIII2LnIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (M = Cr, 1 or Mn, 3) and their isostructural complexes: [MIII2DyIII2(μ3-OH)2(p-Me-PhCO2)6(L)2] (M = Fe, 5 or Al, 7) are discussed and compared. To understand the experimental observations for this family, DFT and ab initio CASSCF + RASSI-SO calculations were performed. The experimental and theoretical calculations suggest that altering the 3dIII ions can affect the single-ion properties and the nature and the magnitude of the 3dIII-3dIII, 3dIII-DyIII and DyIII-DyIII magnetic coupling, thus quenching the quantum tunneling of magnetisation (QTM) significantly, thereby improving the SMM properties within this motif. This is the first systematic study looking at variation and therefore role of trivalent transition metal ions, as well as the diamgnetic AlIII ion, on slow relaxation of magnetisation within a series of isostructural 3d-4f butterfly compounds.

Coordination Clusters of 3d-Metals That Behave as Single-Molecule Magnets (SMMs): Synthetic Routes and Strategies.

The area of 3d-metal coordination clusters that behave as Single-Molecule Magnets (SMMs) is now quite mature within the interdisciplinary field of Molecular Magnetism. This area has created a renaissance in Inorganic Chemistry. From the synthetic Inorganic Chemistry viewpoint, the early years of “try and see” exercises (1993–2000) have been followed by the development of strategies and strict approaches. Our review will first summarize the early synthetic efforts and routes for the preparation of polynuclear 3d-metal SMMs, and it will be then concentrated on the description of the existing strategies. The former involve the combination of appropriate 3d-metal-containing starting materials (simple salts with inorganic anions, metal cardoxylates, and pre-formed carboxylate clusters, metal phosphonates) and one or two primary organic ligands; the importance of the end-on azido group as a ferromagnetic coupler in 3d-metal SMM chemistry will be discussed. The utility of comproportionation reactions and the reductive aggregation route for the construction of manganese SMMs will also be described. Most of the existing strategies for the synthesis of SMMs concern manganese. These involve substitution of carboxylate ligands in pre-formed SMMs by other carboxylate or non-carboxylate groups, reduction procedures for the {} SMMs, spin “tweaking,” “switching on” SMM properties upon conversion of low-spin clusters into high-spin ones, ground-state spin switching and enhancing SMM properties via targeted structural distortions, the use of radical bridging ligands and supramolecular approaches. A very useful strategy is also the “switching on” of SMM behavior through replacement of bridging hydroxide groups by end-on azido or isocyanato ligands in clusters. Selected examples will be mentioned and critically discussed. Particular emphasis will be given on the criteria for the choice of ligands.