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.

Temperature-dependent NIR-CPL spectra of chiral Yb(III) complexes.

Chiral, enantiopure Yb(III) complexes exhibit circularly polarized luminescence (CPL) in the near infrared (NIR) wavelength region. This CPL is quantified by the dissymmetry factor (glum). The excited state 2F5/2 consists of six mJ' states degenerated in three Stark levels, due to the crystal-field splitting (CFS), which are populated in accordance with the Boltzmann distribution. Consequently, room temperature CPL spectra are the sum of various - either positive or negative - contributions, that are practically impossible to quantify. To address this issue, an advanced setup enabling CPL measurements over a broad temperature range (300 to 4 K) has been developed. The interrelation of CFS, glum and temperature was explored using a pair of enantiopure Yb(III) complexes, highlighting the individual contribution of each crystal-field sublevel to the overall CPL spectrum, as anticipated by simulations performed in the framework of multireference wave-functions. Hence, the CPL spectra of chiral lanthanide complexes were found to be indeed strongly temperature-dependent, as is the glum dissymmetry factor, as a consequence of the variation in thermal sublevel population.

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.

Pressure-Induced Structural, Optical and Magnetic Modifications in Lanthanide Single-Molecule Magnets.

Lanthanide Single-Molecule Magnets are fascinating objects that break magnetic performance records with observable magnetic bistability at the boiling temperature of liquid nitrogen, paving the way for potential applications in high-density data storage. The switching of lanthanide SMM has been successfully achieved using several external stimuli such as redox reaction, pH titration, light irradiation or solvation/desolvation thanks to the high sensitivity of the magnetic anisotropy to any structural change in the lanthanide surrounding. Nevertheless, the use of applied high pressure as an external stimulus is largely underused, especially considering that it can be combined with high pressure X-ray diffraction to establish a complementary structure-property relationship. This Concept article summarizes the few relevant examples of investigations of lanthanide SMMs under applied high pressure, provides conclusions on the effect of such stimulus on molecular structures and magnetic anisotropy, and finally draws perspective on the future development of magnetic measurements under applied pressure.

Field induced single ion magnet behavior in CoII complexes in a distorted square pyramidal geometry.

We report three CoII-based complexes with the general formula [CoII(L)(X)2] by changing the halide/pseudo-halide ions [X = NCSe (1SeCN); Cl (2Cl) and Br (3Br)]. The obtained τ5 and CShM values confirm a distorted square pyramidal geometry around the CoII ion in all these complexes. In these three complexes, the central CoII ion is situated above the basal plane of the square pyramidal geometry. The extent of distortion from the ideal SPY-5 geometry differs upon changing the coordinating halide/pseudo-halide ion in these complexes. This essentially results in the alteration of the anisotropic parameter D and hence impacts the magnetic properties in these complexes. This phenomenon has been corroborated with the aid of theoretical investigations. All these complexes display field-induced SIM behaviour with magnetic relaxation occurring through a combination of processes depending on the applied dc magnetic field values and dilution.

Magneto-Chiral Dichroism in a One-Dimensional Assembly of Helical Dysprosium(III) Single-Molecule Magnets.

Here we report magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption of a chiral dysprosium(III) coordination polymer. The two enantiomers of [DyIII(H6(py)2)(hfac)3]n [H6(py)2 = 2,15-bis(4-pyridyl)ethynylcarbo[6]helicene; hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate], where the chirality is provided by a functionalized helicene ligand, were structurally, spectroscopically, and magnetically investigated. Magnetic measurements reveal a slow relaxation of the magnetization, with differences between enantiopure and racemic systems rationalized on the basis of theoretical calculations. When the enantiopure complexes are irradiated with unpolarized light in a magnetic field, they exhibit multiple MChD signals associated with the f-f electronic transitions of DyIII, thus providing the coexistence of MChD-active absorptions and single-molecule-magnet (SMM) behavior. These findings clearly show the potential that rationally designed chiral SMMs have in enabling the optical readout of magnetic memory through MChD.

Single-Molecule Magnet Properties in 3d4f Heterobimetallic Iron and Dysprosium Complexes Involving Hydrazone Ligand.

The reaction between the ((E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide) (H2opch) ligand and the metallo-precursor [Dy(hfac)3]·2H2O led to the formation of an homometallic coordination complex with the formula [Dy2(hfac)3(H2O)(Hopch)2][Dy(hfac)4] (1). In presence of both [Dy(hfac)3] 2H2O and the Fe(II) salt, the heterobimetallic tetranuclear [FeDy3(hfac)8(H2O)2(opch)2] (2) was isolated, while the addition of the co-ligand 1,2-Bis(2-hydroxy-3-methoxybenzylidene) hydrazine (H2bmh) led to the formation of two heterobimetallic tetranuclear complexes with the formula [Fe3Dy(hfac)6(opch)2(H2bmh)] C6H14 (3) C6H14 and [Fe2Dy2(hfac)7(opch)2(H2bmh)] 0.5C7H16 (4) 0.5C7H16. Single crystal X-ray diffraction and dc magnetic investigation demonstrated that 3 and 4 involved the iron center in the +II and +III oxidation states. Dynamic magnetic measurements highlighted the single-molecule magnet behavior of 1 and 2 in a zero applied dc field primarily due to the ferromagnetic interactions taking place in these compounds.

Lanthanoid coordination prompts unusually distorted pseudo-octahedral NiII coordination in heterodinuclear Ni-Ln complexes: synthesis, structure and understanding of magnetic behaviour through experiment and computation.

In this work, a new family of binuclear NiII-LnIII complexes with the formula [NiLn(L)2(NO3)3]·0.5H2O (Ln = Gd, 1; Tb, 2; Dy, 3; Ho, 4; Er, 5; Yb, 6; Y, 7) was synthesized using a thioether group-bearing Schiff base. Due to the strict hard/soft dichotomy between the 4f and 3d metal ions, selective coordination of NiII and 4f metal ions was achieved with the adjacent soft ONS and hard OO binding pockets of the ligand. All the complexes 1-7 exhibit a NiII centre in a distorted pseudo-octahedral geometry with the LnIII centres in distorted bicapped square-antiprism geometry. The huge distortion around the NiII centres is triggered for the accommodation of larger lanthanoids to the adjacent OO coordination site, and this forces the NiII centres to have a tridentate coordination from the ONS, as intermediate between meridional and facial binding. Field-induced single-molecule magnetic behaviour was observed for heterodinuclear complexes involving Kramers lanthanide ions (LnIII = Dy, Er and Yb), with magnetic relaxation occurring through an Orbach process only for 5. DFT calculations using various functionals (BP86, B3LYP, PBE0, TPSSh, PWPB95, R2SCAN) were applied to calculate the isotropic exchange, showing good agreement with the experiment (JGd-Ni = +1.78 cm-1). CASSCF calculations for NiII and LnIII ions were also performed to reveal detailed information about their electronic structure and magnetic anisotropy, supporting the experimental observations. This study accentuates the mutual distortion of coordination geometry induced by flexibility of the ligand backbone with the simultaneous binding of two different metal ions.

Isotopic enrichment in lanthanide coordination complexes: contribution to single-molecule magnets and spin qudit insights.

Lanthanide Single-Molecule Magnets (SMMs) fascinate the scientific community due to their plethora of potential applications ranging from data storage to spintronic devices and quantum computing. This review article proposes a comprehensive description of the influence of the nuclear spin, i.e. hyperfine interaction, on the magnetic properties of lanthanide SMMs and on quantum information processing of qudit. This influence is analysed for non-Kramers and Kramers lanthanide SMMs as well as for the electronic distribution of the electron in 4f orbitals i.e. oblate and prolate ions. Then the role of magnetic interactions in isotopically enriched polynuclear Dy(III) SMMs is discussed. Finally the possible effect of superhyperfine interaction due to the nuclear spin of elements originating from the surrounding of the lanthanide centre is analyzed. The effect of nuclear spin on the dynamics of the lanthanide SMMs is demonstrated using different techniques such as magnetometry, muon spectroscopy (µ-SR), and Mössbauer and Resonance Vibrational Spectroscopies.

Tunable bandgaps in self-assembled transition metal-incorporated heterometallic M2Sb4 (M = V, Mn, Co, Ni, and Cu) oxo clusters.

This paper investigates the reactivity and optical properties of transition metal-incorporated organoantimony(V) clusters prepared by a solvothermal route. The detailed structural characterization of novel heterometallic M2Sb4 oxo clusters is reported herein. Single crystal X-ray diffraction revealed the formation of hexanuclear organoantimony(V) based oxo clusters [(p-ClC6H4Sb)4V2(O)2(µ3-O)2(µ2-O)2(t-BuPO3)4(µ2-OCH3)4] (1), [M2(p-iPr-C6H4Sb)4(µ3-O)2(µ2-O)2(µ2-OCH3)4(t-BuPO3)4(py)2]·xCH3OH, where M = Mn, x = 2 (2), Co, x = 1 (3), Ni, x = 2 (4) and Cu, x = 2 (5). The magnetic behaviour of the clusters was probed by magnetic susceptibility measurements. Optical absorption studies showed that bandgap reduction can be achieved by incorporating an appropriate transition metal into the homometallic Sb6 oxo cluster.

Circularly polarized luminescence in the one-dimensional assembly of binaphtyl-based Yb(iii) single-molecule magnets.

Lanthanide ions have attracted great interest owing to their optical and magnetic properties. Single-molecule magnet (SMM) behavior has been a fascinating science for thirty years. Moreover, chiral lanthanide complexes allow the observation of remarkable circularly polarized luminescence (CPL). However, the combination of both SMM and CPL behaviors in a single molecular system is very rare and deserves attention in the design of multifunctional materials. Four chiral one-dimensional coordination compounds involving 1,1'-Bi-2-naphtol (BINOL)-derived bisphosphate ligands and the Yb(iii) centre were synthesized and characterized by powder and single-crystal X-ray diffraction. All the Yb(iii)-based polymers displayed field-induced SMM behavior with magnetic relaxation occurring by applying Raman processes and near infrared CPL in the solid state.

Tailored Lewis Acid Sites for High-Temperature Supported Single-Molecule Magnetism.

Generating or even retaining slow magnetic relaxation in surface immobilized single-molecule magnets (SMMs) from promising molecular precursors remains a great challenge. Illustrative examples are organolanthanide compounds that show promising SMM properties in molecular systems, though surface immobilization generally diminishes their magnetic performance. Here, we show how tailored Lewis acidic Al(III) sites on a silica surface enable generation of a material with SMM characteristics via chemisorption of (Cpttt)2DyCl ((Cpttt)- = 1,2,4-tri(tert-butyl)-cyclopentadienide). Detailed studies of this system and its diamagnetic Y analogue indicate that the interaction of the metal chloride with surface Al sites results in a change of the coordination sphere around the metal center inducing for the dysprosium-containing material slow magnetic relaxation up to 51 K with hysteresis up to 8 K and an effective energy barrier (Ueff) of 449 cm-1, the highest reported thus far for a supported SMM.

Reversible Pressure-Magnetic Modulation in a Tetrathiafulvalene-Based Dyad Piezochromic Dysprosium Single-Molecule Magnet.

The extreme sensitivity of trivalent lanthanide ions to crystal field variations led to the emergence of single-molecule magnetic switching under various stimuli. The use of pressure as an external stimulus instead of classic light irradiation, oxidation or any chemical reactions allows a fine tuning of the magnetic modulation. Here the well-known pure isotopically enriched [162 Dy(tta)3 (L)]⋅C6 H14 (162 Dy) Single-Molecule Magnet (SMM) (tta- =2-2-thenoyltrifluoroacetonate and L=4,5-bis(propylthio)-tetrathiafulvalene-2-(2-pyridyl)benzimidazole-methyl-2-pyridine) was experimentally investigated by single-crystal diffraction and squid magnetometry under high applied pressures. Both reversible piezochromic properties and pressure modulation of the slow magnetic relaxation behavior were demonstrated and supported by ab initio calculations. The magnetic study of the diluted sample [162 Dy0.05 Y0.95 (tta)3 (L)]⋅C6 H14 (162 Dy@Y) indicated that variations in the electronic structure have mainly intermolecular origin with weak intramolecular contribution. Quantitative magnetic interpretation concludes to a deterioration of the Orbach process for the benefit of both Raman and QTM mechanisms under applied pressure.

Multifunctional Helicene-Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism.

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units (hfac- =1,1,1,5,5,5-hexafluoroacetylaconate), efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a single-molecule magnet (SMM) behaviour and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Bulky anion effect on the architecture of chiral dysprosium single-molecule magnets.

The interest for chiral tris(ß-diketonato)lanthanide complexes in coordination chemistry is huge due to its Lewis acid character, optical activity, and the control of the final compound architecture. The reaction of equimolar quantities of [Dy((-)/(+)hfc)3 (H2 O)] (hfc- = 3-(heptafluoropropylhydroxymethylene)-(+/-)-camphorate) and L led to the formation of a pair of enantiomers for dinuclear complexes [Dy((-)/(+)hfc)3 (L)]2 ⋅C7 H16 ([(-)/(+)1]⋅C7 H16 ) (L = 4'-(4'''-pyridyl-N-oxide)-1,2':6'1''-bis-(pyrazolyl)pyridine]). Starting from the previous experimental protocol with the addition of bulky BArF anions, a partial dissociation of the chiral [Dy((-)/(+)hfc)3 (H2 O)] was observed leading to the isolation of a mono-dimensional cationic chiral polymer {[Dy((-)/(+)hfc)2 (L)][BarF]}n ⋅nCH3 NO2 ([(-)/(+)2]n ⋅nCH3 NO2 ). Natural circular dichroism (NCD) highlighted an exciton CD couplet for [(-)/(+)2]n but not for (-)/(+)1. The latter behaves as a single-molecule magnet (SMM) with a blocking temperature up to 4 K, whereas [(-)/(+)2]n is a 1D assembly of field-induced SMMs with a magnetic relaxation occurring through a Raman process only.

Modulation of the magnetic and photophysical properties in 3d-4f and 4f-4f' heterobimetallic complexes involving a tetrathiafulvalene-based ligand.

The reaction between the 2-(1-(2,6-di(pyrazol-1-yl)-4-methylpyridyl)-4,5-(4,5-bis(propylthio)-tetrathiafulvalenyl)-1H-benzimidazol-2-yl)-pyridine ligand (L), 1 equivalent of Ln(hfac)3·2H2O/Dy(tta)3·2H2O (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta- = 2-thenoyltrifluoroacetonate) and M(hfac)2·2H2O leads to the formation of heteroleptic 3d-4f dinuclear complexes of formula [MLn(hfac)5(L)]n (M(II) = Cd, Zn, Co, Mn, Ni and Ln(III) = Dy, Yb, Nd) and [ZnDy(tta)2(hfac)3(L)]·(CH2Cl2). Their X-ray structures reveal that the two coordination sites are occupied by one Ln(III) ion and one M(II) transition metal respectively. The M(II) ions are coordinated to the benzoimidazolylpyridine (bzip) moiety in a N2O4 coordination sphere, while the Ln(III) ions are coordinated to the 2,6-di(pyrazol-1-yl)-4-pyridine (dpp) moiety in a N3O6 surrounding. When Dy(III) ion is used a field-induced Single-Molecule Magnet (SMM) behavior is detected with a magnetic relaxation time slightly dependent to the nature of the vicinal divalent transition metal. On the other hand, when the Yb(III) is used, intense, moderated or quenched 2F5/2 → 2F7/2 NIR luminescence is observed when the Yb(III) ion is respectively associated with the Zn(II), Mn(II) and Ni(II)/Co(II) ion. The emission intensity can be modulated in function of the metal-to-ligand charge transfer and d-d transition intensities. The replacement of the divalent transition metal by a trivalent lanthanide leads to the formation of heteroleptic 4f-4f' dinuclear complexes of formula [Ln2-xLn'x(hfac)6(L)]·a(CH2Cl2)·b(C6H14) and [Dy1.11Nd0.89(tta)3(hfac)3(L)]. The coordination selectivity is based on the radius. Among the 4f-4f' series, the Dy(III) derivatives displayed such ion in N2O6 eight-coordinated sphere allowing the observation of SMM behavior. The three compounds [Dy1.21Nd0.79(hfac)6(L)]·2(CH2Cl2)·(C6H14), [Yb1.04Nd0.96(hfac)6(L)] and [YbPr(hfac)6(L)] displayed respectively Nd(III), modarated Yb(III) and intense Yb(III) NIR emissions.

Cyclooctatetraenide-based single-ion magnets featuring bulky cyclopentadienyl ligand.

We report a family of organometallic rare-earth complexes with the general formula (COT)M(Cpttt) (where (COT)2- = cyclooctatetraenide, (Cpttt)- = 1,2,4-tri(tert-butyl)cyclopentadienide, M = Y(iii), Nd(iii), Dy(iii) and Er(iii)). Similarly to the prototypical Er(iii) analog featuring pentamethylcyclopentadienyl ligand (Cp*)-, (COT)Er(Cpttt) behaves as a single-ion magnet. However, the introduction of the sterically demanding (Cpttt)- imposes geometric constraints that lead to a simplified magnetic relaxation behavior compared to the (Cp*)- containing complexes. Consequently, (COT)Er(Cpttt) can be viewed as a model representative of this organometallic single-ion magnet architecture. In addition, we demonstrate that the increased steric profile associated with the (Cpttt)- ligand permits preparation, structural characterization and interrogation of magnetic properties of the early-lanthanide complex, (COT)Nd(Cpttt). Such a mononuclear derivative could not be obtained when a (Cp*)- ligand was employed, a testament to larger ionic radius of this early lanthanide ion.

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1'-bi-2-naphtol-derived bisphosphate ligands.

The interest for lanthanide circularly polarized luminescence (CPL) has been quickly growing for 10 years. However, very few of these studies have involved correlation between the dissymmetry factor (glum ) and the chemical modifications in a series of chiral ligands. Four polymeric compounds of Eu(III) were prepared by using a series of binaphtyl derivatives for which the size of the π system as well as the number of stereogenic elements (i.e., the binaphtyl moiety) are modulated. The resulting {[Eu(hfac)3 ((S)/(R)-Lx )]}n (x = 1 and 3) and {[Eu(hfac)3 ((S,S,S)/(R,R,R)-Lx )]}n (x = 2 and 4) have been characterized by powder X-ray diffraction by comparison with the X-ray structures on single crystal of the Dy(III) analogs. In solution, the structure of the complexes is deeply modified and becomes monomeric. The nature of the ligand induces change in the shape of the CPL spectra in CH2 Cl2 solution. Furthermore, a large |glum | = 0.12 of the magnetic-dipole transition for the [Eu(hfac)3 ((S,S,S)/(R,R,R)-L2 )] complex involving the ligand with three stereogenic elements and an extended 𝜋 system has been measured. This report also shows CPL measurements in solid state for the series of {[Eu(hfac)3 ((S)/(R)-Lx )]}n (x = 1 and 3) and {[Eu(hfac)3 ((S,S,S)/(R,R,R)-Lx )]}n (x = 2 and 4) polymers.

Study of the influence of nuclear spin and dilution over the slow relaxation in a 3d4f heterobimetallic single-molecule magnet.

The effects of isotopic enrichment and magnetic dilution have been investigated in a heterobimetallic complex of formula [Zn2L2ADyCl3]·2H2O (ADyZn2) (A = 162 and 163) presenting slow relaxation of the magnetization. Isotopic substitution for 162Dy (I = 0) and 163Dy (I = 5/2) leads to a shift in the relaxation times depending on the suppression or enhancement of the hyperfine interactions. The release of the dipolar interactions through magnetic dilution in a Y(iii)-based matrix enhances the slow relaxation of the magnetization and the visibility of the nuclear spin effect. A comparison of the hysteresis loop at 0.5 K for bulk and diluted analogues of pure isotopically enriched complexes suggested a role of the nuclear spin in the interaction between the active system and the matrix.

Azide-Coordination in Homometallic Dinuclear Lanthanide(III) Complexes Containing Nonequivalent Lanthanide Metal Ions: Zero-Field SMM Behavior in the Dysprosium Analogue.

A series of homometallic dinuclear lanthanide complexes containing nonequivalent lanthanide metal centers [Ln2(LH2)(LH)(CH3OH)(N3)]·xMeOH·yH2O [1, Ln = DyIII, x = 0, y = 2; 2, Ln = TbIII, x = 1, y = 1] have been synthesized [LH4 = 6-((bis(2-hydroxyethyl)amino)-N'-(2-hydroxybenzylidene)picolinohydrazide] and characterized. The dinuclear assembly contains two different types of nine-coordinated lanthanide centers, because the nonequivalent binding of the azide co-ligand as well as the varying coordination of the deprotonated Schiff base ligand. Detailed magnetic studies have been performed on the complexes 1 and 2. Complex 1 and its diluted analogue (15%) are zero-field SMMs with effective energy barriers (Ueff) of magnetization reversal equal to 59(3) K and 66(3) K and relaxation times of τ0 = 10(4) × 10-6 s and 10(4) × 10-8 s, respectively. On the other hand, complex 2 shows a field-induced SMM behavior. Combined ab initio and density functional theory calculations were performed to explain the experimental findings and to unravel the nature of the magnetic anisotropy, exchange-coupled spectra, and magnetic exchange interactions between the two lanthanide centers.