Single-molecule Magnet Behavior Research Articles

High magnetization reversal barriers in luminescent dysprosium octahedral and pentagonal bipyramidal single-molecule magnets based on fluorinated alkoxide ligands.

We report the synthesis and structures of three luminescent dysprosium(iii) complexes based on fluorinated alkoxide ligands of formulas [Dy(L1)2(THF)4][BPh4]·0.5THF (1), [Dy(L2)2(THF)5][BPh4]·2.5THF (2) and [Dy(L3)2(THF)5][BPh4]·2THF (3) (L1 = (CF3)3CO-, L2 = C6F5C6F4O-, L3 = C6F5C(CH3)O-). Despite the different dysprosium ion geometries (octahedral vs. distorted pentagonal bipyramidal), these systems exhibit a single-molecule magnet (SMM) behavior, but with distinct relaxation dynamics. Moreover, a typical dysprosium-based luminescence is observed for the three complexes, which make them bifunctional magneto-luminescent SMMs. Remarkably, complex 3 exhibits a high anisotropy barrier of 1469 cm-1 and a blocking temperature of 22 K, making it one of the most performant alkoxide-based SMMs with the highest blocking temperature for a luminescent SMM.

Alignment of axial anisotropy of a mononuclear hexa-coordinated Co(II) complex in a lattice shows improved single molecule magnetic behavior over a 2D coordination polymer having a similar ligand field.

Two CoII based complexes namely [Co(IAP)(SCN)2] (1) and {[Co(IPEH)2(SCN)2]·H2O}n (2) (where IPEH = (((1E,2E)-1,2-bis(1-(4-(1H-imidazol-1-yl)phenyl)ethylidene)hydrazine) and IAP = (4'-(imidazol-1-yl)acetophenone)) have been synthesized and characterized by single-crystal X-ray diffraction, magnetic measurements and ab initio calculations. Structural analysis revealed that complex 1 has a zero-dimensional mononuclear structure and complex 2 has a two-dimensional framework where the CoII centers are bridged by bis(monodentate) ligand IPEH. In both the complexes, the CoII center has a distorted octahedral geometry with a CoN6 coordination environment, formed by four equatorial N atoms from the neutral ligand and two NCS- at the axial positions. Detailed magnetic measurements reveal the presence of easy-plane magnetic anisotropy for both the complexes, whereas the field-induced slow relaxation of magnetization is observed at a relatively higher temperature in 1 (above 2 K, Ueff = 30 K) as compared to 2 (below 2 K, Ueff = 6.5 K). The ab initio calculations show the negligible effect of the first coordination sphere as similar anisotropic parameters are obtained for both the complexes. Additionally, it was found that the anisotropic axes are aligned well in a particular direction in complex 1 whereas it is randomly oriented in the framework of 2. The parallel orientation of the anisotropic axes enhances the axial anisotropy and reduces the transverse component, resulting in a higher energy barrier (Ueff = 30 K) in complex 1. The detailed analysis of field and temperature dependence of relaxation time indicates that Raman, direct and QTM processes mainly play an important role in the relaxation dynamics of complex 1.

Luminescent dysprosium single-molecule magnets made from designed chiral BINOL-derived bisphosphate ligands

The nature of the aromatic system and the number of chiral centers of the BINOL derived bisphosphate ligands influence both the chiroptical properties and single-molecule magnet behavior of a series of dysprosium-based chains.

Structure, Magnetic Refrigeration Property and Single-Molecule Magnetic Behavior of Three Asymmetric Ln2 (LnIII = Gd, Tb and Dy) Compounds

Structure, Magnetic Refrigeration Property and Single-Molecule Magnetic Behavior of Three Asymmetric Ln2 (LnIII = Gd, Tb and Dy) Compounds

Sensitive magnetic-field-response magnetization dynamics in a one-dimensional dysprosium coordination polymer

A Dy(iii) coordination polymer shows significant single-molecule magnet behavior with a sensitive low-field response.

Single-molecule magnets within polyoxometalate-based frameworks.

As an extension of our interest in polyoxometalates (POMs) and lanthanoids, we report the design and synthesis of two polyoxometalate-based frameworks under hydrothermal conditions; [Ho4(PDA)4(H2O)11][(SiO4)@W12O36]·8H2O (1) and [Tb4(PDA)4(H2O)12][(SiO4)@W12O36]·4H2O (2) (H2PDA = 1,10-phenanthroline-2,9-dicarboxylic acid). Both hybrids have been characterized by elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and powder/single-crystal X-ray diffraction. According to the structural analysis, 1 and 2 consist of 2D-cationic coordination polymers based on the respective lanthanoids and PDA2- as well as Keggin anions that reside in the interspaces between two adjacent layers as discrete counterions connected by extensive hydrogen bonding. Although the overall structures of 1 and 2 are composed of cationic and anionic layers, there are many differences in the cationic layers such as various coordination modes of PDA2-, different void shapes, and the existence of dinuclear Tb(III) units only in 2. Frameworks 1 and 2 were further characterized by dc and ac magnetic measurements and both exhibit slow relaxation of magnetization at low temperatures under an applied dc field. Their single-molecule magnet (SMM) properties are investigated, where weak field-induced SMM behaviour is observed at low temperatures in dynamic magnetic studies.

Tetrairon(II) extended metal atom chains as single-molecule magnets.

Iron-based extended metal atom chains (EMACs) are potentially high-spin molecules with axial magnetic anisotropy and thus candidate single-molecule magnets (SMMs). We herein compare the tetrairon(ii), halide-capped complexes [Fe4(tpda)3Cl2] (1Cl) and [Fe4(tpda)3Br2] (1Br), obtained by reacting iron(ii) dihalides with [Fe2(Mes)4] and N2,N6-di(pyridin-2-yl)pyridine-2,6-diamine (H2tpda) in toluene, under strictly anhydrous and anaerobic conditions (HMes = mesitylene). Detailed structural, electrochemical and Mössbauer data are presented along with direct-current (DC) and alternating-current (AC) magnetic characterizations. DC measurements revealed similar static magnetic properties for the two derivatives, with χMT at room temperature above that for independent spin carriers, but much lower at low temperature. The electronic structure of the iron(ii) ions in each derivative was explored by ab initio (CASSCF-NEVPT2-SO) calculations, which showed that the main magnetic axis of all metals is directed close to the axis of the chain. The outer metals, Fe1 and Fe4, have an easy-axis magnetic anisotropy (D = -11 to -19 cm-1, |E/D| = 0.05-0.18), while the internal metals, Fe2 and Fe3, possess weaker hard-axis anisotropy (D = 8-10 cm-1, |E/D| = 0.06-0.21). These single-ion parameters were held constant in the fitting of DC magnetic data, which revealed ferromagnetic Fe1-Fe2 and Fe3-Fe4 interactions and antiferromagnetic Fe2-Fe3 coupling. The competition between super-exchange interactions and the large, noncollinear anisotropies at metal sites results in a weakly magnetic non-Kramers doublet ground state. This explains the SMM behavior displayed by both derivatives in the AC susceptibility data, with slow magnetic relaxation in 1Br being observable even in zero static field.

Magnetic slow relaxation of Tb(III) complex with a nitronyl nitroxide involving a brominated-pyridyl substituent

A new nitronyl nitroxide-Tb(III) complex, [Tb(hfac)3(NIT-3-Br-4Py)2] (1) (hfac = hexafluoroacetyl -acetonate, NIT-3-Br-4Py = 2-(3′-bromo-4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), has been synthesized and characterized. The single-crystal X-ray diffraction analysis shows it crystallizes in monoclinic C2/c space group, and is composed of mononuclear molecules. The central Tb(III) ion is eight-coordinated by three bidentate chelating hfac anions and two monodentate NITR ligands, with a dodecahedron environment. Ac magnetic susceptibility study shows that complex 1 exhibits slow magnetic relaxation, suggesting single-molecule magnet behavior.

Ten-Coordinate Lanthanide [Ln(HL)(L)] Complexes (Ln = Dy, Ho, Er, Tb) with Pentadentate N3O2-Type Schiff-Base Ligands: Synthesis, Structure and Magnetism

A series of five neutral mononuclear lanthanide complexes [Ln(HL)(L)] (Ln = Dy3+, Ho3+ Er3+ and Tb3+) with rigid pentadentate N3O2-type Schiff base ligands, H2LH (1-Dy, 3-Ho, 4-Er and 6-Tb complexes) or H2LOCH3, (2-Dy complex) has been synthesized by reaction of two equivalents of 1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))dibenzohydrazine (H2LH, [H2DAPBH]) or 1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))di-4-methoxybenzohydrazine (H2LOCH3, [H2DAPMBH]) with common lanthanide salts. The terbium complex [Tb(LH)(NO3)(H2O)2](DME)2 (5-Tb) with one ligand H2LH was also obtained and characterized. Single crystal X-ray analysis shows that complexes 1–4 have the composition {[Ln3+(HL)−(L)2−] solv} and similar molecular structures. In all the compounds, the central Ln3+ ion is chelated by two interlocked pentadentate ligands resulting in the coordination number of ten. Each lanthanide ion is coordinated by six nitrogen atoms and four oxygen atoms of the two N3O2 chelating groups forming together a distorted bicapped square antiprismatic polyhedron N6O4 with two capping pyridyl N atoms in the apical positions. The ac magnetic measurements reveal field-induced single-molecule magnet (SMM) behavior of the two dysprosium complexes (with barriers of Ueff = 29 K at 800 Oe in 1-Dy and Ueff = 70 K at 300 Oe in 2-Dy) and erbium complex (Ueff = 87 K at 1500 Oe in 4-Er); complex 3-Ho with a non-Kramers Ho3+ ion is SMM-silent. Although 2-Dy differs from 1-Dy only by a distant methoxy-group in the phenyl ring of the ligand, their dynamic magnetic properties are markedly different. This feature can be due to the difference in long-range contributions (beyond the first coordination sphere) to the crystal-field (CF) potential of 4f electrons of Dy3+ ion that affects magnetic characteristics of the ground and excited CF states. Magnetic behavior and the electronic structure of Ln3+ ions of 1–4 complexes are analyzed in terms of CF calculations.

Probing the Magnetic Anisotropy of Co(II) Complexes Featuring Redox-Active Ligands.

Coordination complexes that possess large magnetic anisotropy (otherwise known as zero-field splitting, ZFS) have possible applications in the field of magnetic materials, including single molecule magnets (SMMs). Previous studies have explored the role of coordination number and geometry in controlling the magnetic anisotropy and SMM behavior of high-spin (S = 3/2) Co(II) complexes. Building upon these efforts, the present work examines the impact of ligand oxidation state and structural distortions on the spin states and ZFS parameters of pentacoordinate Co(II) complexes. The five complexes included in this study (1-5) have the general formula, [Co(TpPh2)(LX,Y)]n+ (X = O, S; Y = N, O; n = 0 or 1), where TpPh2 is the scorpionate ligand hydrotris(3,5-diphenyl-pyrazolyl)borate(1-) and LX,Y are bidentate dioxolene-type ligands that can access multiple oxidation states. The specific LX,Y ligands used herein are 4,6-di-tert-butyl substituted o-aminophenolate and o-aminothiophenolate (1 and 2, respectively), o-iminosemiquinonate and o-semiquinonate radicals (3 and 4, respectively), and o-iminobenzoquinone (5). Each complex exhibits a distorted trigonal bipyramidal geometry, as revealed by single-crystal X-ray diffraction. Direct current (dc) magnetic susceptibility experiments confirmed that the complexes with closed-shell ligands (1, 2, and 5) possess S = 3/2 ground states with negative D-values (easy-axis anisotropy) of -41, -78, and -30 cm-1, respectively. For 3 and 4, antiferromagnetic coupling between the Co(II) center and o-(imino)semiquinonate radical ligand results in S = 1 ground states that likewise exhibit very large and negative anisotropy (-100 > D > -140 cm-1). Notably, ZFS was measured directly for each complex using far-infrared magnetic spectroscopy (FIRMS). In combination with high-frequency and -field electron paramagnetic resonance (HFEPR) studies, these techniques provided precise spin-Hamiltonian parameters for complexes 1, 2, and 5. Multireference ab initio calculations, using the CASSCF/NEVPT2 approach, indicate that the strongly negative anisotropies of these Co(II) complexes arise primarily from distortions in the equatorial plane due to constrictions imposed by the TpPh2 ligand. This effect is further amplified by cobalt(II)-radical exchange interactions in 3 and 4.

Lanthanide Complexes with a Tripodal Nitroxyl Radical Showing Strong Magnetic Coupling.

A series of isomorphous mononuclear complexes of Ln(III) ions comprising one stable tripodal oxazolidine nitroxyl radical were obtained in acetonitrile media starting from nitrates. The compounds, [LnRad(NO3)3] (Ln = Gd, Tb, Dy, Tm, Y; Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl), have a molecular structure. Their coordination polyhedron, LnO7N2, can be described as a tricapped trigonal prism with symmetry not far from D3h. The extracted value of 23 cm-1 for the antiferromagnetic coupling of Gd-Rad established from the DC magnetic and EPR data is a record strength for the complexes of 4f elements with nitroxyl radicals. The terbium derivative displays frequency-dependent out-of-phase signals in zero field, indicating single-molecule magnetic behavior. With an applied field of 0.1 T, an effective barrier of 57 cm-1 is found.

Structure, fluorescence properties and slow magnetic relaxation of Dy2 and Tb4 clusters

Two new Ln(III)-based clusters, namely [Dy2(acac)2(HL)2(H2O)2] (1) and [Tb4(L)4(CH3OH)4]•3CH3OH•H2O (2) (H3L = 2-hydroxy-N'-[(1E)-(8-hydroxyquinolin-2-yl)methylidene]benzohydrazide, and Hacac = acetylacetone), were successfully synthesized by employing a polydentate Schiff base ligand (H3L) under solvothermal conditions. The structures and magnetic properties of clusters 1 and 2 have been systematacially investigated. Single crystal X-ray diffraction indicates that cluster 1 is a dinuclear structure, whereas cluster 2 displays a novel Tb4 tetrahedral arrangement. Magnetic studies reveal that cluster 1 exhibits single-molecule magnets (SMMs) behavior under zero dc filed (ΔE/kB = 48.1 K, and τ0 = 3.63 × 10−7 s), while no SMM behavior was observed in cluster 2.

A tetranuclear DyIII compound with in situ oxazolidine ligand derived from hydroxyquinoline carboxaldehyde: Synthesis, structure, and SMM behavior

Tetranuclear dysprosium(III) complex [Dy4(HL3)4(CH3COO)4(EtOH)2] (1) (H3L3 = 2-(4,4-bis(hydroxymethyl)oxazolidin-2-yl)quinolin-8-ol) was synthesized from 8-hydroxyquinoline-2-carbaldehyde (HL1), 2-amino-2-(hydroxymethyl)propane-1,3-diol (H3L2) ligands and Dy(CH3COO)3·6H2O in CH3OH and CH3CH2OH mixed solvent. The H3L3 ligand was obtained by the in situ Schiff base reaction of HL1 with H3L2 followed by the in situ cyclisation reaction catalyzed by Dy(III) ions. This is the first example of in situ cyclisation reactions of oxazolidine catalyzed by Dy(III) ion during the formation of complex. AC magnetic susceptibility measurements showed that complex 1 exhibited an obvious single-molecule magnetic behavior, which energy barrier was 37.3 (2) K under zero dc-field.

Crystal structure and single-molecule magnet behavior of a novel tetranuclear Dy(III)-based cluster

By using a polydentate Schiff base ligand (H3L), in this paper, a new Dy(III)-based cluster, namely [Dy4(HL)4(CH3O)4]·4CH3OH (1), was successfully obtained and further characterized by single-crystal X-ray diffraction. The crystal structure measurement suggests that cluster 1 crystallizes in the monoclinic space group C2/c and the four center Dy(III) ions of cluster 1 displays a tetrahedral arrangement. The magnetic study reveals that cluster 1 shows remarkable single-molecule magnet (SMM) behavior under zero dc filed (ΔE/kB = 54.6 K, and τ0 = 6.43 × 10−7 s).

Water Molecule-Induced Reversible Magnetic Switching in a Bis-Terpyridine Cobalt(II) Complex Exhibiting Coexistence of Spin Crossover and Orbital Transition Behaviors.

The development of molecule-based switchable materials remains an important challenge in the field of molecular science. Achievement of a structural phase transition induced by adsorption/desorption of guest molecules in spin crossover (SCO) Co(II) compounds is of significant interest because of the possibility that the spin state of the magnetic anisotropic high-spin (HS, S = 3/2) and low-spin (LS, S = 1/2) states can be switched via the induced changes in associated intermolecular interactions. In this study, we demonstrated a reversible magnetic switching associated with spin state conversion, along with a single-crystal to single-crystal (SCSC) phase transition induced by dehydration/rehydration. [Co(terpy)2](BF4)2·H2O (1·H2O; terpy = 2,2':6',2''-terpyridine) assembles in the solid state via π-π and CH-π interactions involving adjacent terpyridine cores along the ab direction to form two-dimensional (2D) layered domains. 1·H2O exhibits gradual and incomplete SCO, from fully HS to ca. 0.5 HS, and the field-induced single-molecule magnet (SMM) behavior attributed to the presence of the anisotropic partial high-spin Co(II) species. 1·H2O undergoes a SCSC transformation accompanied by a change from the tetragonal space group I41/a to P42/n via a dehydration process. Dehydrated 1 exhibits a reverse thermal hysteresis behavior (T1/2↑ = 287 K; T1/2↓ = 270 K) in the gradual SCO region from fully HS to ca. 0.5 HS, followed by an ordinary thermal hysteresis (T'1/2↑ = 195 K; T'1/2↓ = 155 K) to fully LS Co(II). A temperature-dependent single-crystal X-ray structural analysis revealed that the reverse hysteresis can be attributed to an order/disorder structural phase transition of the BF4- anions involving a symmetry breaking to yield the monoclinic space group P21/n and orbital (angular momentum) transition (LT). Both the SCSC phase transition and magnetic behavior are switchable by dehydration/rehydration processes; thus 1 again adsorbs water at room temperature to give both the original structure and its magnetic behavior.

Modulating Magnetic and Photoluminescence Properties in 2-Aminonicotinate-Based Bifunctional Coordination Polymers by Merging 3d Metal Ions.

Herein, the synthesis and study of bifunctional coordination polymers (CPs) with both magnetic and photoluminescence properties, derived from a heterometallic environment, are reported. As a starting point, three isostructural monometallic CPs with the formula [M(μ-2ani)2 ]n (MII =Mn (1Mn ), Co (3Co ) and Ni (4Ni ); 2ani=2-aminonicotinate), crystallise as chiral 2D-layered structures stacked by means of supramolecular interactions. These compounds show high thermal stability in the solid state (above 350 °C), despite which, in aqueous solution, compound 1Mn is shown to partially transform into a novel 1D chain CP with the formula [Mn(2ani)2 (μ-H2 O)2 ]n (2Mn ). A study of the direct current (dc) magnetic properties of 1Mn , 3Co and 4Ni reveals a spin-canted structure derived from antisymmetric antiferromagnetic weak exchanges along the chiral network (as confirmed by DFT calculations) and magnetic anisotropy of the ions, in such a way that long-range ordering is observed with variable magnitude for the spin carriers. Moreover, compounds 3Co and 4Ni show no frequency-dependent alternating current (ac) susceptibility curves under zero dc field; this is characteristic behaviour of a glassy state that may be partially supressed for 3Co by applying an external dc field. To overcome long-range magnetic ordering, CoII ions are diluted in a diamagnetic ZnII -based matrix, which enables single-molecule magnet behaviour. Interestingly, this strategy allows a bifunctional Cox Zn1-x 2ani material, which is imbued with a strong photoluminescent emitting capacity, as characterised by an intense blue light followed by a green afterglow, to be obtained.

Multifunctional Binuclear Ln(III) Complexes Obtained viaIn SituTandem Reactions: Multiple Photoresponses to Volatile Organic Solvents and Anticounterfeiting and Magnetic Properties

The design and synthesis of simple lanthanide complexes with multiple functions have been widely studied and have faced certain challenges. Herein, we successfully synthesized the series of binuclear lanthanide complexes [Ln2(L1)2(NO3)4] (HL1 = 2-amino-1,2-bis(pyridin-2-yl)ethanol; Ln = Dy (Dy2), Tb (Tb2), Ho (Ho2) Er (Er2)) via the in situ self-condensation of Ln(NO3)3·6H2O-catalyzed 2-aminomethylpyridine (16 steps) under solvothermal conditions. Dy2 was mixed with different volatile organic solvents, and photoluminescence tests demonstrated that it showed an excellent selective photoresponse to chloroform (CHCl3). Sensing Tb2 on different organic solvents under the same conditions showed that it exhibited excellent selective photoresponse to methanol (CH3OH). Even under EtOH conditions, Tb2 could selectively respond to small amounts of CH3OH. To the best of our knowledge, achieving a selective photoresponse to various volatile organic compounds by changing the metal center of the complex is difficult. Furthermore, we performed anticounterfeiting tests on Tb2, and the results showed significant differences between the anticounterfeiting marks under white light and ultraviolet light conditions. The alternating current susceptibilities of Dy2 suggested that it was a typical single-molecule magnet (SMM) (Ueff = 93.62 K, τ0 = 1.19 × 10-5 s) under a 0 Oe dc field. Ab initio calculations on Dy2 indicated that the high degrees of axiality of the constituent mononuclear Dy fragments are the main reasons for the existence of SMM behavior.

Coordination-enhanced photochromism in dysprosium dinuclear complexes with photomodulated single-molecule magnet behavior

We report the synthesis of a pyrazine-based bis-tridentate diarylethene (DAE) ligand and the corresponding dinuclear yttrium and dysprosium complexes that all show T-type photochromism. Large changes in the photochromic behaviour are induced by metal coordination, including a tuning of the bleaching rate by several orders of magnitude, characterized through VT-NMR and supported by theoretical calculations. The dysprosium dinuclear complex shows a single-molecule magnet (SMM) behaviour, under an external applied magnetic field, significantly modulated upon photoisomerization. This feature is further analyzed through ab initio calculations.

Slow Magnetic Relaxation of a 12-Metallacrown-4 Complex with a Manganese(III)-Copper(II) Heterometallic Ring Motif.

The heterobimetallic metallacrown (MC), (TMA)2{Mn(OAc)2[12-MCMn(III)Cu(II)N(shi)-4](CH3OH)}·2.90CH3OH, 1, where TMA+ is tetramethylammonium, -OAc is acetate, and shi3- is salicylhydroximate, consists of a MnII ion captured in the central cavity and alternating unambiguous and ordered manganese(III) and copper(II) sites about the MC ring, a first for the archetypal MC structure design. DC-magnetometry characterization and subsequent simulation with the Spin Hamiltonian H = -J1(s1 + s3)·s5 - J2(s2 + s4)·s5 - J3Σi=14si·si+1 + d(sz,12 + sz,32) + μBΣj=15gjsj·B indicates an S = 5/2 ground state and a sizable axial zero-field splitting on MnIII. AC-susceptibility measurements reveal that 1 displays slow magnetization relaxation akin to single-molecule magnet (SMM) behavior.

Redox Modulation of Field-Induced Tetrathiafulvalene-Based Single-Molecule Magnets of Dysprosium

The complexes [Dy2(tta)6(H2SQ)] (Dy-H2SQ) and [Dy2(tta)6(Q)]·2CH2Cl2 (Dy-Q) (tta− = 2-thenoyltrifluoroacetonate) were obtained from the coordination reaction of the Dy(tta)3·2H2O units with the 2,2′-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate ligand (H2SQ) and its oxidized form 2,2′-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione (Q). The chemical oxidation of H2SQ in Q induced an increase in the coordination number from 7 to 8 around the DyIII ions and by consequence a modulation of the field-induced Single-Molecule Magnet behavior. Computational results rationalized the magnetic properties of each of the dinuclear complexes.