Single-molecule Magnet Behavior Research Articles

Synergism of Light-Induced [4 + 4] Cycloaddition and Electron Transfer Toward Switchable Photoluminescence and Single-Molecule Magnet Behavior in a Dy4 Cubane.

Molecular materials possessing switchable magneto-optical properties are of great interest due to their potential applications in spintronics and molecular devices. However, switching their photoluminescence (PL) and single-molecule magnet (SMM) behavior via light-induced structural changes still constitutes a formidable challenge. Here, a series of cubane structures were synthesized via self-assembly of 9-anthracene carboxylic acid (HAC) and rare-earth ions. All complexes exhibited obvious photochromic phenomena and complete PL quenching upon Xe lamp irradiation, which were realized via the synergistic effect of photogenerated radicals and [4 + 4] photocycloaddition of the AC components. The quenched PL showed the largest fluorescence intensity change (99.72%) in electron-transfer photochromic materials. A reversible decoloration process was realized via mechanical grinding, which is unexpectedly in the electron-transfer photochromic materials. Importantly, an SMM behavior of the Dy analog was observed after room-temperature irradiation due to the photocycloaddition of AC ligands and the photogenerated stable radicals changed the electrostatic ligand field and magnetic coupling. Moreover, based on the remarkably photochromic and photoluminescent properties of these compounds, 2 demos were applied to support their application in information anti-counterfeiting and inkless printing. This work, for the first time utilizing the simultaneous modulation of photocycloaddition and photogenerated radicals in one system, realizes complete PL quenching and light-induced SMM behavior, providing a dynamical switch for the construction of multifunctional polymorphic materials with optical response and optical storage devices.

Cu(II)-Ln(III) (Ln = Gd, Tb and Dy) complexes of an unsymmetrical N2O3 donor ligand: field induced SMM behaviour of Cu(II)-Tb(III) complexes.

Three new hetero-metallic CuII-LnIII complexes [(CuL)Gd(NO3)3(CH3OH)]n (1), [(CuL)Tb(NO3)3(H2O)]·[CuL] (2) and [(CuL)Dy(NO3)3(H2O)]·[CuL] (3) have been synthesized using a mono-nuclear Cu(II) complex, [CuL], of an unsymmetrically di-condensed N2O3 donor Schiff base ligand, N-(3-methoxysalicylidene)-N-(salicylidene)-1,2-ethylenediamine (H2L). Single crystal X-ray crystallography revealed that complex 1 is a nitrate bridged 1D chain of dinuclear Cu(II)-Gd(III) units whereas in 2 and 3, the dinuclear Cu(II)-Ln(III) units are co-crystallized with a [CuL] unit. The Ln(III) centers are nine coordinated with the geometry of a spherical capped square antiprism for Gd and spherical tricapped trigonal prism for Tb and Dy. The geometry of the Cu(II) center is distorted octahedral for complex 1 and distorted square planar for complexes 2 and 3. Temperature-dependent molar magnetic susceptibility measurements in 1-3 revealed the presence of overall ferromagnetic coupling between the Cu(II) and Ln(III) centers. Notably, field induced single-molecule magnet behavior was witnessed in the Tb(III) derivative (2). The ab initio calculations indicated that upon application of an external magnetic field, the tunneling in the ground state of complex 2 gets reduced and thereby field-induced SMM behaviour is observed. Besides, in the case of complex 1, BS-DFT calculations were carried out to gain further insights into the magnetic exchange coupling interactions between the Cu(II) and Gd(III) centers.

Dy4 and Dy5 complexes based on tautomeric hydrazone Schiff-base ligand regulated by temperature showing single-molecule magnet behaviour

Two dysprosium complexes [Dy4(H2L)6]⋅4H2O (Dy4) and [Dy5(H2L)(HL)2(L)(µ3OH)2Cl(H2O)(MeCN)2]⋅4MeOH⋅7H2O (Dy5) (H4L = (N',N'''E,N',N'''E)-N',N'''-(pyridine-2,6-diylbis(methanylylidene))bis(2-hydroxybenzohydrazide)) based on hydrazone Schiff-base ligand were synthesized, which could be regulated by controlling temperature (Dy4, below 293 K and Dy5, over 308 K). Magnetic studies show that complex Dy4 is a typical field-induced single-molecule magnet with an effective energy barrier (Ueff) of 42.9 K under 1 kOe dc field. Complex Dy5 is a zero dc field single-molecule magnet with an effective energy barrier (Ueff) of 4.18 K. The results indicate the synthesis of lanthanide complexes is sensitive to substitute of ligand and temperature.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] (CotTIPS=1,4-(iPr3Si)2C8H6) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η8-CotTIPS)LnIII(μ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Dy, Er) and [(η8-CotTIPS)ErIII(μ-η6:η6-DEDBA)ErIII(η8-CotTIPS)] exhibit Single-Molecule Magnet (SMM) behaviour. In the case of [(η8-CotTIPS)LnIII(μ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Dy, Er), the introduction of a second near lanthanide ion results in strong antiferromagnetic interactions, allowing the enhancement of the magnetic characteristic of the system, compared to the quasi isolated counterpart. This research renews the overlooked coordination chemistry of the DBA ligand and expands it to encompass rare-earth elements.

Single-Molecule Magnet Behavior of Confined Dy(III) in a Mixed Heteroatom-Substituted Polyoxotungstate.

Two heteroatom-templated Dy(III)-confined polyoxotungstates [H2N(CH3)2]7Na7[Dy2(H2O)7(W4O9)(HPSeW15O54)(α-SeW9O33)2]·31H2O (1) and [H2N(CH3)2]14K2Na18{[Dy2(H2O)13W14O40]2[α-SeW9O33]4[HPSeW15O54]2}·44H2O (2) were synthesized by a one-pot aqueous reaction and structurally characterized. The most distinctive structural feature of complexes 1 & 2 is the simultaneous presence of both trivacant Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building blocks containing P(III)-Se(IV) heteroatoms. The trimeric polyanion of 1 can be represented as a fusion of two trivacant Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building units encapsulating the [Dy2(H2O)7(W4O9)]12+ cluster. On the other hand, hexameric polyoxoanions of 2 are described as four trivacant Keggin [α-SeW9O33]8- and two Dawson [HPSeW15O54]10-, building units anchoring a [Dy4(H2O)26W28O80]20+ cluster. The magnetic investigation revealed the presence of significant magnetic anisotropy and slow relaxation of magnetization behavior for complex 1 with a phenomenological energy barrier, Ueff = 13.58 K in the absence of an external magnetic field, and Ueff = 24.57 K in the presence of a 500 Oe external dc magnetic field. On the other hand, complex 2 favors the QTM relaxation process in the absence of an external magnetic field and shows field-induced slow relaxation of magnetization with Ueff = 11.11 K at 1500 Oe applied dc field. The in-depth analysis of magnetic relaxation dynamics shows that the relaxation process follows the Orbach as well as Raman relaxation pathways. Further, the ab initio calculation of the studied complexes confirms that the highly axial ground and first excited energy states (containing pure highest mJ states) are responsible for the observed single-molecule magnet (SMM) behavior. Remarkably, this is the first example of a mixed heteroatom-based Dy(III)-substituted polyoxotungstate with both trimeric Keggin [α-SeW9O33]8- and Dawson [HPSeW15O54]10- building units showing SMM behavior.

Synthesis and Magnetic Properties of Bis-Halobenzene Decamethyldysprosocenium Cations.

The decamethyldysprosocenium cation, [Dy(Cp*)2]+ (Cp* = {C5Me5}), was a target single-molecule magnet (SMM) prior to the isolation of larger dysprosocenium cations, which have recently shown magnetic memory effects up to 80 K. However, the relatively short Dy···Cp*centroid distances of [Dy(Cp*)2]+, together with the reduced resonance of its vibrational modes with electronic states compared to larger dysprosocenium cations, could lead to more favorable SMM behavior. Here, we report the synthesis and magnetic properties of a series of solvated adducts containing bis-halobenzene decamethyldysprosocenium cations, namely [Dy(Cp*)2(PhX-κ-X)2][Al{OC(CF3)3}4] (X = F or Cl) and [Dy(Cp*)2(C6H4F2-κ2-F,F)(C6H4F2-κ-F)][Al{OC(CF3)3}4]. These complexes were prepared by the sequential reaction of [Dy(Cp*)2(μ-BH4)]∞ with allylmagnesium chloride and [NEt3H][Al{OC(CF3)3}4], followed by recrystallization from parent halobenzenes. The complexes were characterized by powder and single crystal X-ray diffraction, NMR and ATR-IR spectroscopy, elemental analysis, and SQUID magnetometry; experimental data were rationalized by a combination of density functional theory and ab initio calculations. We find that bis-halobenzene adducts of the [Dy(Cp*)2]+ cation exhibit highly bent Cp*···Dy···Cp* angles; these cations are also susceptible to decomposition by C-X (X = F, Cl, Br) activation and displacement of halobenzenes by O-donor ligands. The effective energy barrier to reversal of magnetization measured for [Dy(Cp*)2(PhF-κ-F)2][Al{OC(CF3)3}4] (930(6) cm-1) sets a new record for SMMs containing {Dy(Cp*)2} fragments, though all SMM parameters are lower than would be predicted for an isolated [Dy(Cp*)2]+ cation, as expected due to transverse ligand fields introduced by halobenzenes and the large deviation of the Cp*···Dy···Cp* angle from linearity promoting magnetic relaxation.

A nested spin structure and single molecule magnet behaviour in an Fe8Dy12 heterometallic cyclic coordination cluster.

The 20-nuclearity compound [Fe8Dy12(tea)8(teaH)12(NO3)12]·8MeCN (where teaH3 = triethanolamine) was synthesised and characterised through single crystal X-ray diffraction and magnetic measurements. The shape of the magnetic hysteresis in the microSQUID measurements was rationalised using the MAGELLAN program.

A photochromic trinuclear dysprosium(iii) single-molecule magnet with two distinct relaxation processes.

Multifunctional molecules responsive to light are highly desired as components for the construction of remotely controlled nanodevices. Here we present a DyIII single molecule magnet (SMM) comprising dithienylethene (dte) photochromic bridging ligands in the form of a pyridine (py) derivative: 1,2-bis((2-methyl-5-pyridyl)thie-3-yl)perfluorocyclo-pentene (dtepy). The title trinuclear compound {[DyIII(BHT)3]3(dtepy)2}·4C5H12 (1) was synthesized by combining the low-coordinate dysprosium complexes DyIII(BHT)3 (BHT = 2,6-di-tert-butyl-4-methylphenolate) with dtepy bridging ligands in the 'open' form using n-pentane as a completely inert solvent. The trinuclear molecule comprises two different DyIII centers due to its quasi-linear geometry: a central trigonal bipyramidal DyIII ion and two peripheral ones with an approximate trigonal pyramidal geometry. Thanks to that, 1 shows two types of SMM behavior which is slightly affected by the photoisomerization of the photochromic dtepy bridges. The impact of the photoisomerization on the magnetization dynamics was studied by means of alternating current (AC) magnetic susceptibility measurements for the 'open' and 'closed' forms of the molecules. The changes between the 'open' and 'closed' isomers were further investigated by IR and UV-vis spectroscopy, suggesting the co-existence of the ligand-related photochromism and single-molecule magnet behavior in 1. However, the powder X-ray diffraction studies indicate loss of structural order in the first photoisomerization step preventing in-depth studies.

Single-molecule magnet behavior in heterometallic decanuclear [Ln2Fe8] (Ln = Y, Dy, Ho, Tb, Gd) coordination clusters.

Five decanuclear lanthanide-iron clusters, formulated as [Ln2Fe8(hmp)10(μ2-OH)4(μ3-OH)2(μ4-O)4(H2O)6]·6ClO4·xH2O (x ≈ 8, Ln = Y for 1; x ≈ 6, Ln = Dy for 2; x ≈ 6, Ln = Ho for 3; x ≈ 7, Ln = Tb for 4; x ≈ 7, Ln = Gd for 5, Hhmp = 2-(hydroxymethyl)pyridine), have been synthesized and structurally characterized. Single-crystal structural analysis reveals that the cluster consists of six face-sharing defective cubane units. Dynamic magnetic investigations indicated that cluster 2 exhibits single-molecule magnet behavior under a zero dc field eliciting an effective energy barrier of Ueff = 17.76 K and a pre-exponential factor of τ0 = 7.93 × 10-8 s. Investigation of the performance of a series of FeIII-DyIII SMMs indicates that the relatively low energy barrier in 2 is associated with the weak ferromagnetic coupling between FeIII and DyIII ions, while the strength of ferromagnetic interaction in these clusters is mainly related to the bond distances between DyIII and O atoms coordinated to FeIII ions. Clusters 3 and 4 exhibit similar dual relaxation pathways under their respective optimal external applied dc field, where the direct relaxation process occurs in the low-frequency area, which impedes the extraction of the Ueff, while the secondary relaxation process appears at a higher frequency, which is probably a connection with intermolecularly driven relaxation. Our findings offer a magneto-structural correlation model for further investigating the single-molecule magnet behavior in lanthanide-iron systems.

New series of mononuclear β-diketonate cerium(III) field induced single-molecule magnets.

Five new β-diketonate Ce3+ mononuclear complexes, [Ce(Btfa)3(H2O)2] (1), [Ce(Btfa)3(phen)] (2), [Ce(Btfa)3(bipy)] (3), [Ce(Btfa)3(terpy)] (4) and [Ce(Btfa)3(bathophen)(DMF)] (5), where Btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate, phen = 1,10-phenanthroline, bipy = 2,2'-bipyridyl, terpy = 2,2':6',2''-terpyridine and bathophen = 4,7-diphenyl-1,10-phenanthroline, have been synthesized and structurally characterized through X-ray diffraction of single crystals. The central Ce3+ atom displays a coordination number of 8 for 1, 2 and 3 and of 9 for 4 and 5. Under a 0 T external magnetic field, none of the given compounds exhibits single molecule magnet (SMM) behaviour. However, a small magnetic field, between 0.02 and 0.1 T, is enough for all the compounds to exhibit slow relaxation of the magnetization. A comprehensive magnetic analysis, with experimental magnetic data and ab initio calculations, was undertaken for all the complexes, and the study highlights the significance of the different spin relaxation mechanisms that must be considered for a Ce3+ lanthanide ion.

Tuning the slow magnetic relaxation with the substituents in anilate bridged bis(dysprosium) complexes.

Dinuclear lanthanide complexes [((HB(pz)3)2Dy)2(μ-Th2An)] (1Dy) and [((HB(pz)3)2Dy)2(μ-ClCNAn)] (2Dy), based on the hydrotris(pyrazol-1-yl)borate (HBpz3-) scorpionate capping ligand and anilate (An2-) bridging linkers, namely homosubstituted dithiophene- and heterosubstituted chlorocyanoanilate, bearing electron-donating and withdrawing substituents at the 3,6-positions of the benzoquinone core, are reported. 1Dy shows an octacoordinated {N6O2} DyIII ion within a D4h distorted square antiprismatic coordination, an ideal geometry for Single-Molecule Magnet (SMM) behavior, given its oblate nature, whereas in 2Dy the octacoordinated DyIII ion adopts a D2d triangular dodecahedron geometry, while maintaining the same {N6O2} coordination sphere. Both complexes show field-induced single molecule magnet (SMM) behaviour, with tuning of the slow magnetic relaxation as a function of the nature of the substituents at the 3,6-positions of the anilate moiety. A comparison of the Arrhenius fitting parameters for 1Dy and 2Dy supports the hypothesis that square antiprismatic DyIII complexes, as 1Dy, exhibit higher energy barriers. This interpretation is supported by ab initio calculations that also shed light on the crucial role of intermolecular dipolar interactions.

How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(II) complexes.

A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1-3) and 3 (4); X = I (1), Br (2 and 4) and Cl (3); S = MeCN (1 and 2) and EtOAc (3)] has been synthesised and characterised by single-crystal X-ray diffraction, electron paramagnetic resonance, and static (dc) and dynamic (ac) magnetic measurements combined with theoretical calculations. The structures of 1-4 consist of mononuclear bis(chelating) cobalt(II) complex cations, [CoII(n-XPhPDI)2]2+, perchlorate anions, and acetonitrile (1 and 2) or ethyl acetate (3) molecules of crystallisation. This unique series of mononuclear six-coordinate octahedral cobalt(II) complexes displays both thermally-induced low-spin (LS)/high-spin (HS) transition and field-induced slow magnetic relaxation in both LS and HS states. A complete LS ↔ HS transition occurs for 1 and 2, while it is incomplete for 4, one-third of the complexes being HS at low temperatures. In contrast, 3 remains HS in all the temperature range. 1 and 2 show dual spin relaxation dynamics under the presence of an applied dc magnetic field (Hdc), with the occurrence of faster- (FR) and slower-relaxing (SR) processes at lower (Hdc = 1.0 kOe) and higher fields (Hdc = 2.5 kOe), respectively. On the contrary, 3 and 4 exhibit only SR and FR relaxations, regardless of Hdc. Overall, the distinct field-dependence of the single-molecule magnet (SMM) behaviour along with this family of spin-crossover (SCO) cobalt(II)-n-XPhPDI complexes is dominated by Raman mechanisms and, occasionally, with additional temperature-independent Intra-Kramer [LS or HS (D > 0)] or Quantum Tunneling of Magnetisation mechanisms [HS (D < 0)] also contributing.

In situ hydrolysis of a carbophosphazene ligand leads to one-dimensional lanthanide coordination polymers. Synthesis, structure and dynamic magnetic studies.

An in situ hydrolysis of the P-Cl bonds of the carbophosphazene [{NC(NMe2)}2{NPCl2}] (LPCl2) in the presence of hydrated lanthanide(III) nitrates in a dichloromethane and methanol (2 : 1) solvent mixture afforded a series of novel 1D coordination polymers: [{Ln(LHPO2)3(NO3)2(CH3OH)(H2O)} (Cl)]n {where Ln(III) = Gd (1), Tb (2), Dy (3), or Er (4) and LHPO2 is the hydrolyzed carbophosphazene (LPCl2) ligand}. X-ray crystallographic analysis revealed that complexes 1-4 are isostructural and crystallized in the monoclinic crystal system having P21/c space group. The coordination polymers are formed because of the involvement of the geminal P(O)(OH) moieties of the carbophosphazene ligand. Each lanthanide(III) ion is 9-coordinate (9O) in a distorted muffin geometry. Magnetic measurements revealed that both DyIII and ErIII analogues exhibit field-induced single-molecule magnet (SMM) behavior at 0.8 kOe and 2.2 k Oe, respectively. At such dc fields, the dynamic magnetic susceptibility displays complex behavior with a triple magnetic relaxation contribution for 3, while two contributions were identified for 4. The observed static and dynamic magnetic behavior for complexes 1-4 were further rationalized with the aid of BS-DFT and CASSCF/SO-RASSI/SINGLE_ANISO calculations.

Magneto-structural correlation in lanthanide luminescent [2.2]paracyclophane-based single-molecule magnets.

The association of lanthanide ions and paracyclophane derivatives has been very scarcely reported in the literature. In this study, elaboration of five coordination lanthanide complexes involving the 1,4(1,4)-dibenzenacyclohexaphane-12,43-diylbis(diphenylphosphine oxide) ligand (L) was achieved with the determination of single-crystal X-ray diffraction structures of four mononuclear complexes of formula [Ln(hfac)3(L)] (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate) (Ln = Dy(III) (1-Dy) and Yb(III) (2-Yb)) and [Ln(tta)3(L)] (tta- = 2-tenoyl-trifluoroacetylacetonate) (Ln = Dy(III) (3-Dy) and Yb(III) (4-Yb)) and one dinuclear complex [Na(Dy2(hfac)6(L)2)](BArF) (BArF- = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) (5-Dy). The compounds were characterized using elemental analysis, IR spectroscopy, DC and AC magnetic measurements and photophysical investigations. L is an efficient organic chromophore for the sensitization of both visible Dy(III) (1-Dy) and near-infrared Yb(III) (2-Yb and 4-Yb) luminescence. The combination of excitation and emission spectra allowed the determination of the crystal field spitting of both the 2F7/2 ground state and 2F5/2 excited state for 2-Yb and 4-Yb. Moreover, 3-Dy and the two Yb(III) derivatives displayed field-induced single-molecule magnet (SMM) behaviour with slow magnetic relaxation occurring through the Raman process only for 2-Yb and 4-Yb, whereas a combination of Orbach and Raman processes was identified for 3-Dy.

Two multifunctional Dy(iii)-based metal–organic frameworks exhibiting proton conduction, magnetic properties and second-harmonic generation

Two novelty Dy-MOFs were synthesized using H4DTTP-2OMe ligand. MOF 1 displays a more superior proton conductivity, field-induced single molecule magnets behavior and obvious second-order nonlinear optical properties.

Unlocking single molecule magnetism: a supramolecular strategy for isolating neutral MnIII salen-type dimer in crystalline environments.

In [Mn(5-MeOsalen)(Cl)]2(dibenzo[24]crown-8), dibenzo[24]crown-8 formed a supramolecule via multi-point interactions with the [Mn(5-MeOsalen)(Cl)] dimer. The dimer was magnetically isolated with ST = 4 and weak interdimer magnetic interactions. The crystal exhibited single-molecule magnet behaviour with an anisotropic barrier of 26(1) K, which is the highest among the Mn-salen series reported to date.

Effect of coordinated anions on ferromagnetically coupled Dy2 zero-field single-molecule magnets.

A new hydrazone Schiff base ligand was condensed from 2-hydroxy-3-methoxybenzaldehyde and pyrimidine-4-carbohydrazide {H2L = (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrimidine-4-carbohydrazide}, which was used to assemble two new Dy2 complexes Dy2L2(DMF)2(NO3)2 (1) and Dy2L2(DMF)2(AcO)2 (2). Notably, the coordinated anions have a subtle effect on the coordination configurations of the Dy3+ ions and the magnetic properties of the two Dy2 complexes. The Dy3+ ions in 1 and 2 have the same N2O5 coordination environment but show the triangular dodecahedron and the biaugmented trigonal prism coordination configurations, respectively. Magnetic measurements revealed that both 1 and 2 have intramolecular ferromagnetic interactions between the Dy3+ ions and show single-molecule magnet behaviors at 0 Oe, with Ueff/k values of 58.2 K for 1 and 59.9 K for 2. These magnetic properties may be explained by theoretical calculations.

Endohedral metallofullerene molecular nanomagnets.

Magnetic lanthanide (Ln) metal complexes exhibiting magnetic bistability can behave as molecular nanomagnets, also known as single-molecule magnets (SMMs), suitable for storing magnetic information at the molecular level, thus attracting extensive interest in the quest for high-density information storage and quantum information technologies. Upon encapsulating Ln ion(s) into fullerene cages, endohedral metallofullerenes (EMFs) have been proven as a promising and versatile platform to realize chemically robust SMMs, in which the magnetic properties are able to be readily tailored by altering the configurations of the encapsulated species and the host cages. In this review, we present critical discussions on the molecular structures and magnetic characterizations of EMF-SMMs, with the focus on their peculiar molecular and electronic structures and on the intriguing molecular magnetism arising from such structural uniqueness. In this context, different families of magnetic EMFs are summarized, including mononuclear EMF-SMMs wherein single-ion anisotropy is decisive, dinuclear clusterfullerenes whose magnetism is governed by intramolecular magnetic interaction, and radical-bridged dimetallic EMFs with high-spin ground states that arise from the strong ferromagnetic coupling. We then discuss how molecular assemblies of SMMs can be constructed, in a way that the original SMM behavior is either retained or altered in a controlled manner, thanks to the chemical robustness of EMFs. Finally, on the basis of understanding the structure-magnetic property correlation, we propose design strategies for high-performance EMF-SMMs by engineering ligand fields, electronic structures, magnetic interactions, and molecular vibrations that can couple to the spin states.

Spin dynamics phenomena of a cerium(III) double-decker complex induced by intramolecular electron transfer.

Switchable spin dynamic properties in single-molecule magnets (SMMs) via an applied stimulus have applications in single-molecule devices. Many SMMs containing heavy lanthanoid ions with strong uniaxial magnetic anisotropy have been reported to exhibit SMM characteristics in the absence of an external magnetic field. On the other hand, SMMs containing light lanthanoid cerium(III) (Ce3+) ions exhibit field-induced slow magnetic relaxation. We investigated the chemical conversion of a diamagnetic Ce4+ ion (4f0) to a paramagnetic Ce3+ ion (4f1) in Ce-phthalocyaninato double-decker complexes (TBA+[Ce(obPc)2]- (1) and TBA+[Ce(Pc)2]- (2)) which exhibit field-induced SMM behaviour due to a 4f1 system. The phthalocyaninato ligands with electron-donating substituents (obPc2- = 2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato) in 1 have a significant effect on the valence state of the Ce ion, which is reflected in its magnetic properties due to the mixed valence state of the Ce ion. Given that Ce double-decker complexes with π-conjugated ligands undergo intramolecular electron transfer (IET) to the Ce ion mixed valence state, characterised by a mixture of 4f0 and 4f1 configurations, we examined the dynamic disorder inherent in IET influencing magnetic relaxation.

A magnetic Ni-based metal-organic framework with interesting transformation dynamics

Herein, a flexible system composed of two Ni(II)-based coordination compounds: a 3D framework of {[Ni(μ-3isoani)2]·DMF}n (1) formula and a 0D monomeric [Ni(3isoani)2(H2O)4] (2) complex (where 3isoani = 3-aminoisonicotinato and DMF = dimethylformamide) which show mutual solvent-induced reversible transformations into each other is reported. The system shows reversible 1 ↔ 2 transformations upon the exposure of one compound to the solvent present in the other, that is, the MOF (1) in water and the monomer (2) in DMF. The process is easily followed by the naked eye because it involves a colour change from green (1)-to-brownish green (2), making the process traceable as previously observed for the Co(II)-based system. Moreover, these compounds present very different magnetic properties since 1 shows field-induced single-molecule magnet (SMM) behaviour, which corresponds to one of the few Ni(II)-based compounds showing single-ion behaviour (being Ni(II) the unique spin carrier), whereas 2 behaves as a regular paramagnet, all of which is explained according to a careful study of the magnetic properties by means of experimental direct-current (dc) and alternating-current (ac) measurements. Obtained experimental results are well supported by active space self-consistent field (CASSCF) calculations that allow understanding the slow relaxation occurring in the Ni(II) ion.