Field-induced Slow Relaxation Research Articles

Quantifying Magnetic Anisotropy of Series of Five-Coordinate CoII Ions: Experimental and Theoretical Insights.

Stabilizing large easy-axis type magnetic anisotropy in molecular complexes is a challenging task, yet it is crucial for the development of information storage devices and applications in molecular spintronics. Achieving this requires a deep understanding of electronic structure and the relationships between structure and properties to develop magneto-structural correlations that are currently unexplored in the literature. Herein, a series of five-coordinate distorted square pyramidal CoII complexes [Co(L)(X2)].CHCl3 (where X = Cl (1), Br (2), or I (3)) is reported, all exhibiting easy-axis magnetic anicotropy. The size of the zero field splitting axial parameter (D) is quantitatively determined (1 = -72; 2 = -67 and 3 = -25 cm-1) using a cantilever torque magnetometry which is further firmly supported by magnetic susceptibility, and EPR measurements. The study of the magnetization relaxation dynamics reveals field-induced slow relaxation of magnetization due to the predominant Raman relaxation process. Theoretical calculations on 1-3 and optimized model complexes of 1 reveal insights into the electronic structure and highlight the impact of steric and electronic effects on modulating the D values. Overall, the studies reported pave the way for designing a new generation of CoII complexes with enhanced axiality and a lower rhombicity.

Slow Relaxation of the Magnetisation in a Two-Dimensional Metal–Organic Framework with a Layered Square Lattice

Herein, we present the synthesis and structural characterisation of two layered MOFs with the asymmetric ligand 3-chloro,6-cyano-2,5-dihydroxy-1,4-benzoquinone dianion (C6O4(CN)Cl2− = chlorocyananilato). These compounds, formulated as (H3O)[Eu(C6O4(CN)Cl)2(H2O)]·34H2O (1) and (H3O)[Dy(C6O4(CN)Cl)2(H2O)]·44H2O (2), are isostructural and show a (4,4)-layered square structure with the crystallisation water molecules located between the layers. The lanthanoid ions are surrounded by four bis-bidentate chlorocyananilato ligands that connect each LnIII centre with other four, giving rise to square cavities formed by LnIII centres in the vertices and chlorocyananilato ligands as the sides. There is an additional coordinated water molecule that occupies the caped position of the capped square antiprismatic coordination geometry around the LnIII centres. The magnetic properties show the presence of a field-induced slow relaxation of the magnetisation in the DyIII derivative at low temperatures that follows Direct and Orbach relaxation mechanisms with an energy barrier of 36(3) K.

THz-EPR-based Magneto-Structural Correlations for Cobalt(II) Single-Ion Magnets With Bis-Chelate Coordination.

New cobalt(II)-based complexes with [N2O2] coordination formed by two bis-chelate ligands were synthesized and characterized by a multi-technique approach. The complexes possess an easy-axis anisotropy (D<0) and magnetic measurements show a field-induced slow relaxation of magnetization. The spin-reversal barriers, i. e., the splitting of the two lowest Kramers doublets (UZFS), have been measured by THz-EPR spectroscopy, which allows to distinguish the two crystallographically independent species present in one of the complexes. Based on these experimental UZFS energies together with those for related complexes reported in literature, it was possible to establish magneto-structural correlations. UZFS linearly depends on the elongation parameter ϵT of the (pseudo-)tetrahedral coordination, which is given by the ratio between the average obtuse and acute angles at the cobalt(II) ion, while UZFS was found to be virtually independent of the twist angle of the chelate planes. With increasing deviation from the orthogonality of the latter, the rhombicity (|E/D|) increases.

Bimetallic Ba(II)-Cr(III) and trimetallic Ba(II)-Ln(III)-Cr(III) (Ln(III) = Gd, Tb, Dy, Ho, Er, Yb, Y) coordination polymers formed by Cr(III)-containing building blocks with cyclopropane-1,1-dicarboxylate anions

The reaction of chromium(III) nitrate with Ba(cpdc) (H2cpdc = cyclopropane-1,1-dicarboxylic acid) in a ratio of 1:3 yielded a 1D coordination polymer {[Ba2Cr2(OH)2(cpdc)4(H2O)8]·5H2O}n (1) formed by binuclear units [Cr2(OH)2(cpdc)4]4− and a 3D polymer [Ba2Cr(cpdc)3(NO3)(H2O)6]n (2) constructed from tris-chelate blocks [Cr(cpdc)3]3−. The addition of rare-earth metal nitrates (Cr:Ln = 1:2) in this reaction led to the formation of a series of trimetallic 3D coordination polymers {[Ba3Ln2Cr4(cpdc)12(H2O)24]·8H2O}n (3Ln, Ln = Gd, Tb, Dy, Ho, Er, Yb, Y), in whose structures tris-chelate fragments [Cr(cpdc)3]3− are bound in layers by Ln3+ ions and, further, in a framework due to the coordination of Ba2+ ions. The crystal structures of 1, 2, and 3Gd were determined by single-crystal X-ray diffraction (XRD), and isostructurality of all the compounds in the series 3Ln was proved by powder X-ray diffraction (PXRD). DC-magnetic susceptibility measurements revealed weak ferromagnetic exchange interactions between Cr3+ ions in compound 1 (J = +0.74 cm−1). According to ac-magnetic susceptibility measurements, complexes 3Er and 3Y exhibit field-induced slow relaxation of magnetization. According to the data of simultaneous thermal analysis (STA) and differential scanning calorimetry (DSC) performed under Ar atmosphere, dehydration of the compounds obtained takes place in one (for 1 and 3Gd) or three stages (for 2). The initial temperature of the organic part degradation process decreases when moving from compound 1 containing dimerized bis-chelate fragments [Cr2(OH)2(cpdc)4]4− (330 °C) to compounds 2 (276 °C) and 3Gd (261 °C) based on tris-chelate units [Cr(cpdc)3]3−.

Anilato-Based Coordination Polymers with Slow Relaxation of the Magnetization: Role of the Synthetic Method and Anilato Ligand.

We have prepared and characterized three coordination polymers formulated as [Dy2(C6O4Cl2)3(fma)6] ⋅ 4.5fma (1) and [Dy2(C6O4X2)3(fma)6] ⋅ 4fma ⋅ 2H2O with X=Br (2) and Cl (3), where fma=formamide and C6O4X2 2-=3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion with X=Cl (chloranilato) and Br (bromanilato). Compounds 1 and 3 are solvates obtained with slow and fast precipitation methods, respectively. Compounds 2 and 3 are isostructural and only differ in the X group of the anilato ligand. The three compounds present (6,3)-gon two-dimensional hexagonal honey-comb structures. Magnetic measurements indicate that the three compounds show slow relaxation of the magnetization at low temperatures when a continuous magnetic field is applied, although with different relaxation times and energy barriers depending on X and the crystallisation molecules. Compounds 1-3 represent the first examples of anilato-based lattices with formamide and field-induced slow relaxation of the magnetization.

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.

Influence of the phonon-bottleneck effect and low-energy vibrational modes on the slow spin-phonon relaxation in Kramers-ions-based Cu(II) and Co(II) complexes with 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and dicyanamide.

Two new complexes, bis-[4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole-κ2N2,N6]bis-(dicyanamide-κN8)copper(II), [Cu(abpt)2(dca)2] (1) and bis-[4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole-κ2N2,N6]bis-(dicyanamide-κN8)cobalt(II), [Co(abpt)2(dca)2] (2), have been prepared and magneto-structurally characterised. Single crystal studies of both complexes have shown that their crystal structures are molecular, in which the central atoms are six-coordinated in the form of a distorted octahedron by two bidentate abpt and two monodentate dca ligands. Even if both complexes have the same composition and crystallize in the same P1̄ space group, they are not isostructural. Both structures contain strong intermolecular N-H⋯N hydrogen bonds and π-π stacking interactions. IR spectra are consistent with the solved structures of both complexes and confirmed the terminal character of the dca ligands and the bidentate coordination of the abpt ligands. The analysis of the magnetic properties showed that both complexes exhibit field-induced slow spin-phonon relaxation. In both complexes, the slow spin-phonon relaxation is influenced by a severe phonon-bottleneck effect that affects the direct process, a dominant relaxation mechanism at low temperatures in both complexes. The phonon-bottleneck effect in 1 was suppressed by simply reducing the crystallite size, and further analysis of the field dependence of the relaxation time yielded the characteristic energy of vibrational modes of 11 cm-1 participating in the Raman process at low magnetic fields. The analysis of magnetic properties and ab initio calculations confirmed that 2 represents a system with a moderate uniaxial anisotropy yielding an average energy barrier of 82 cm-1 (from all four nonequivalent Co(II) sites in the structure of 2).

Photoluminescent and Magnetic Properties of Mononuclear Lanthanide-Based Compounds Containing the Zwitterionic Form of 4-Picolinic Acid as a Ligand

A series of mononuclear lanthanide-based coordination compounds was obtained under mild synthetic conditions and fully characterized. Single-crystal X-ray diffraction reveals six isomorphic compounds of type [Ln(NO3)(4picH)2(H2O)4](NO3)2 (Ln3+ = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Er (6)), in which 4picH is the zwitterionic form of the 4-picolinic acid. Except for compounds 3 and 6, a study into the emissive properties of the compounds was carried out, revealing a ligand-sensitized lanthanide-characteristic luminescence. Compounds 2 and 4 are candidates for luminescent probes in solution. At the same time, the chromaticity data for 5 revealed a potential white-light emitter with a correlated color temperature (CCT) value of 6570 K. Alternating current (AC) magnetic susceptibility measurements, supported by theoretical calculations, showed a field-induced slow relaxation of the magnetization and a single-ion magnet behavior for compound 5.

Control of the geometry and anisotropy driven by the combination of steric and anion coordination effects in CoII complexes with N6-tripodal ligands: the impact of the size of the ligand on the magnetization relaxation time.

Four mononuclear CoII complexes of formula [Co(L)(SCN)2(CH3OH)0.5(H2O)0.5]·1.5H2O·0.75CH3OH (1), [Co(L1)Cl2]·H2O·2CH3CN (2), [Co(L1)(SCN)2]·1.5H2O·CH3OH (3) and [Co(L1)]ClO4·2CH3OH (4) were prepared from the N6-tripodal Schiff base ligands (S)P[N(Me)NC(H)2-Q]3 (L) and (S)P[N(Me)NC(H)1-ISOQ]3 (L1), where Q and ISOQ represent quinolyl and isoquinolyl moieties, respectively. In 1, the L ligand does not coordinate to the CoII ion in a tripodal manner but using a new N,N,S tridentate mode, which is due to the fact that the N6-tripodal coordination promotes a strong steric hindrance between the quinolyl moieties. However, L1 can coordinate to the CoII ions either in a tripodal manner using CoII salts with poorly coordinating anions to give 4 or in a bisbidentate fashion using CoII salt-containing medium to strongly coordinating anions to afford 2 and 3. In the case of L1, there is no steric hindrance between ISOQ moieties after coordination to the CoII ion. The CoII ion exhibits a distorted octahedral geometry for compounds 1-3, with the anions in cis positions for the former and in trans positions for the two latter compounds. Compound 4 shows an intermediate geometry between an octahedral and trigonal prism but closer to the latter one. DC magnetic properties, HFEPR and FIRMS measurements and ab initio calculations demonstrate that distorted octahedral complexes 1-3 exhibit easy-plane magnetic anisotropy (D > 0), whereas compound 4 shows large easy-axis magnetic anisotropy (D < 0). Comparative analysis of the magneto-structural data underlines the important role that is played not only by the coordination geometry but also the electronic effects in determining the anisotropy of the CoII ions. Compounds 2-3 show a field-induced slow relaxation of magnetization. Despite its large easy-axis magnetic anisotropy, compound 4 does not show significant slow relaxation (SMR) above 2 K under zero applied magnetic fields, but its magnetic dilution with ZnII triggers SMR at zero field. Finally, it is worth remarking that compounds 2-4 show smaller relaxation times than the analogous complexes with the tripodal ligand bearing in its arms pyridine instead of isoquinoline moieties, which is most likely due to the increase of the molecular size in the former one.

Modulated spin dynamics of [Co2] coordination helicates via differential strand composition.

Coordination supramolecular chemistry provides a versatile entry into materials with functionalities of technological relevance at the nanoscale. Here, we describe how two different bis-pyrazolylpyridine ligands (L1 and L2) assemble with Co(II) ions into dinuclear triple-stranded helicates, in turn, encapsulating different anionic guests. These constructs are described as (Cl@[Co2(L1)3])3+, (SiF6@[Co2(L1)(L2)3])2+ and (ClO4@[Co2(L2)3])3+, as established by single-crystal X-ray diffraction. Extensive magnetic and calorimetric measurements, numerical treatments and theoretical calculations reveal that the individual Co(II) centers of these supramolecular entities exhibit field-induced slow relaxation of magnetization, dominated by direct and Raman mechanisms. While the small variations in the spin dynamics are not easily correlated with the evident structural differences among the three species, the specific heat measurements suggest two vibronic pathways of magnetic relaxation: one that would be associated with the host lattice and another linked with the guest.

Investigation of slow magnetic relaxation in a series of 1D polymeric cyclobutane-1,1-dicarboxylates based on LnIIIVIV2 units (LnIII = Tb, Dy, Ho, Er, Tm, Yb): rare examples of VIV-4f single-molecule magnets.

The reactions of VOSO4·3H2O with Na2(cbdc) (cbdc2- - dianion of cyclobutane-1,1-dicarboxylic acid) and lanthanide(III) nitrates taken in a molar ratio of 1 : 2 : 1 were found to yield a series of isostructural heterometallic compounds [NaLn(VO)2(cbdc)4(H2O)10]n (1Ln, Ln = Tb, Dy, Ho, Er, Tm, Yb). These compounds are constructed from trinuclear anionic units [Ln(VO)2(cbdc)4(H2O)8]- ({LnV2}-) linked by Na+ ions into 1D polymeric chains. The crystal structures of 1Dy and 1Er were determined by single-crystal X-ray diffraction (XRD), and their isostructurality with 1Tb, 1Ho, 1Tm, and 1Yb was proved by powder X-ray diffraction (PXRD). According to alternating current (ac) magnetic susceptibility measurements, 1Dy, 1Er, and 1Yb exhibited field-induced slow relaxation of magnetization. Compound 1Er is the first representative of ErIII-VIV single-molecule magnets. Measuring the temperature dependences of the phase memory time (Tm) for 1Dy and 1Yb using pulsed EPR spectroscopy allowed us to observe the phenomenon of phase relaxation enhancement (PRE) at temperatures below 30 K. In future, this phenomenon may contribute to the evaluation of relaxation times of the lanthanide ions.

Magnetic anisotropy and slow relaxation of magnetisation in double salts containing four- and six-coordinate cobalt(II) complex ions.

Four novel Co(II) coordination compounds 1-4 of the general formula [Co(Ln)2][Co(NCY)4]·mCH3CN (where Ln are tridentate ligands L1 = 2,6-bis(1-hexyl-1H-benzimidazol-2-yl)pyridine for 1 and 2; L2 = 2,6-bis(1-octyl-1H-benzimidazol-2-yl)pyridine for 3; L3 = 2,6-bis(1-dodecyl-1H-benzimidazol-2-yl)pyridine for 4, Y = O for 1, 3, and 4 and Y = S for 2; m = 0 for 1 and 3, m = 0.5 for 2 and m = 2 for 4) were prepared and characterised. The molecular structures of all four compounds consist of the hexacoordinate complex cation [Co(Ln)2]2+ and tetracoordinate complex anion [Co(NCY)4]2-, with distorted octahedral and tetrahedral symmetry of coordination polyhedra, respectively. The electronic structures of all compounds feature an orbitally non-degenerate ground state well-separated from the lowest excited state, which allows the analysis of the magnetic anisotropy by the spin Hamiltonian model. ZFS parameters, derived from both CASSCF-NEVPT2 calculations and magnetic data analysis, indicate that tetrahedral anions [Co(NCY)4]2- exhibit small axial parameters |D| spanning the range of 2.2 to 7.7 cm-1, while octahedral cations [Co(Ln)2]2+ display significantly larger |D| parameters in the range of 37 to 95 cm-1. For 1-3, the Fourier-transform infrared magnetic spectroscopy (FIRMS) revealed a reasonable transmission with a magnetic absorption around the expected value for the ZFS accompanied by features allowing to identify phonon frequencies and simulate spin-phonon couplings. Dynamic magnetic investigations unveiled the field-induced slow relaxation of magnetisation, with maximal relaxation times (τ) of 92(2) μs for 2 at 2 K and BDC = 0.3 T. The temperature evolution of τ was analysed using a combination of Orbach, direct and Raman relaxations (Ueff = 8(1) K (5.6 cm-1)) or Orbach, direct and spin-phonon induced relaxations (Ueff = 10.3(9) K (7.2 cm-1)). The rest of the complexes, namely 1, 3, and 4 show field-induced slow relaxation of magnetisation with τ smaller than 16 μs.

Slow magnetization relaxation of a high-spin iron(iii) in mayenite Ca12Al14O33

High-spin Fe3+ ion imbedded in the extended solid displays field-induced slow relaxation of magnetization with enhanced relaxation time values.

Field-induced Co(II) single-ion magnet in octahedral [S6] coordination environment

The soft donor ligands are of great importance to the pursuit of 3d transition-metal complexes with large magnetic anisotropy. Herein, a soft tripodal ligand, hydrotris(mercaptobenzothiazolyl)borate (Tbz) was used to construct a high-spin mononuclear complex [CoII(Tbz)2] (1), having an octahedral geometry in an S6 donor set. The combination of direct-current (dc) magnetic susceptibility and Low-temperature high-field electron paramagnetic resonance (HFEPR) reveals the easy-axis magnetic anisotropy of 1. Complex 1 shows field-induced slow relaxation of magnetization at an applied magnetic field of 1000 Oe, indicating the behavior of single-molecule magnet. The foregoing result constitutes the first instance of Co(II)-based single-ion magnet containing a CoS6 unit.

Two families of Ln(III)-V(IV) compounds (Ln(III) = Eu, Tb, Dy, Ho) of different structural types mediated by Rb+ and Cs+ cations: Slow magnetic relaxation of Eu(III)- and Ho(III)-containing members

The reactions of oxidovanadium(IV) sulfate with Rb2(cbdc) or Cs2(cbdc) (cbdc2− – dianion of cyclobutane-1,1-dicarboxylic acid) and lanthanide(III) nitrates in water solutions gave two series of heterometallic compounds, namely {[RbLn(VO)2(cbdc)4(H2O)10]·2.5H2O}n (1Ln, Ln = Eu, Tb, Dy, Ho) and {[CsLn(VO)2(cbdc)4(H2O)11]·5H2O}2 (2Ln, Ln = Eu, Tb, Dy, Ho), respectively. The crystal structures of these compounds were determined by X-ray diffraction and were found to be built of similar trinuclear anionic units [Ln(VO)2(cbdc)4(H2O)8]− ({LnV2}−). Due to the structure-forming role of alkali metal ions, the heterometallic {LnV2} cores of these units differ in geometric characteristics (the V⋯Ln and V⋯V distances) and spatial arrangement in a crystal. In 1Ln, the {LnV2}− units are bound by rubidium ions into a 3D framework structure, whereas in 2Ln, cesium ions provide the formation of a discrete molecular structure. According to alternating current (ac) magnetic susceptibility measurements, only Eu(III)- and Ho(III)-containing compounds (1Eu, 1Ho, 2Eu, and 2Ho) exhibited field-induced slow relaxation of magnetization.

Slow relaxation of the magnetization in two cobalt(iii)/cobalt(ii) dimers

The magnetic properties of two CoIIICoII dimers with the CoIIIO2CoII cores show a field-induced slow relaxation of the magnetization following Direct, Orbach and Raman mechanisms.

Layered lanthanide phosphonates Ln(2-qpH)(SO4)(H2O)2 (Ln = La, Ce, Pr, Nd, Sm): polymorphism and magnetic properties.

Polymorphic layered lanthanide coordination polymers provide opportunities to study the effect of intralayer and interlayer interactions on their magnetic dynamics. Herein we report a series of layered lanthanide phosphonates, namely, α-Ln(2-qpH)(SO4)(H2O)2 (Ln = Sm) (α-Ln), β-Ln(2-qpH)(SO4)(H2O)2 (Ln = Pr, Nd, Sm) (β-Ln) and γ-Ln(2-qpH)(SO4)(H2O)2 (Ln = La, Ce, Pr, Nd, Sm) (γ-Ln) (2-qpH2 = 2-quinolinephosphonic acid), which crystallize in monoclinic P21/c (α-Ln), triclinic P1̄ (β-Ln) and orthorhombic Pbca (γ-Ln) space groups, respectively. The structural differences between the β- and γ-phases lie not only in the intralayer but also in the interlayer. Within the layers, the Ln2O2 dimers are aligned parallel in the β-phase, but are non-parallel in the γ-phase. In the interlayer, there are π-π interactions between the quinoline groups in the α- and β-phases but not in the γ-phase. Magnetic studies reveal a field-induced slow relaxation of the magnetisation at low temperatures for compounds γ-Ce, β-Nd, and γ-Nd, and the impact of polymorphism on the magnetic dynamics of Nd(III) compounds is discussed.

Two-dimensional dysprosium(III) coordination polymer: Structure, single-molecule magnetic behavior, proton conduction, and luminescence.

A new dysprosium (III) coordination polymer [Dy(Hm-dobdc) (H2O)2]·H2O (Dy-CP), was hydrothermal synthesized based on 4,6-dioxido-1,3-benzenedicarboxylate (H4m-dobdc) ligand containing carboxyl and phenolic hydroxyl groups. The Dy(III) center adopts an octa-coordinated [DyO8] geometry, which can be described as a twisted square antiprism (D 4d symmetry). Neighboring Dy(III) ions are interconnected by deprotonated Hm-dobdc3− ligand to form the two-dimensional infinite layers, which are further linked to generate three-dimensional structure through abundant hydrogen bonds mediated primarily by coordinated and lattice H2O molecules. Magnetic studies demonstrates that Dy-CP shows the field-induced slow relaxation of magnetization and the energy barrier U eff/k B and relaxation time τ 0 are 35.3 K and 1.31 × 10–6 s, respectively. Following the vehicular mechanism, Dy-CP displays proton conductivity with σ equal to 7.77 × 10–8 S cm−1 at 353 K and 30%RH. Moreover, luminescence spectra reveal that H4m-dobdc can sensitize characteristic luminescence of Dy(III) ion. Herein, good magnetism, proton conduction, and luminescence are simultaneously achieved, and thus, Dy-CP is a potential multifunctional coordination polymer material.

Stable Lanthanide Metal-Organic Frameworks with Ratiometric Fluorescence Sensing for Amino Acids and Tunable Proton Conduction and Magnetic Properties.

Four new isostructural lanthanide metal-organic frameworks (MOFs), namely {[Ln(DMTP-DC)1.5(H2O)3]·DMF}n [H2DMTP-DC = 2',5'-dimethoxytriphenyl-4,4″-dicarboxylic acid; LnIII = EuIII (1), GdIII (2), TbIII (3), and DyIII (4)], have been synthesized and characterized. Single-crystal structure analysis reveals that 1-4 are three-dimensional Ln-MOFs with rich H-bonding of coordinated H2O molecules in the network channels. The X-ray diffraction patterns indicate that Ln-MOF 1 displays good stabilities in organic solvents and aqueous solutions with distinct pH values. Both 1 and 3 show characteristic emission of LnIII ions. Ln-MOF 1 can be used as a ratiometric fluorescence sensor for arginine and lysine in aqueous solution, and the detection limits are 24.38 μM for arginine and 9.31 μM for lysine. All 1-4 show proton conductivity related to relative humidity (RH) and temperature, and the maximum conductivity values of 1-4 at 55 °C and 100% RH are 9.94 × 10-5, 1.62 × 10-4, 1.71 × 10-4, and 2.67 × 10-4 S·cm-1, respectively. The value of σ increases with the decrease in ionic radius, indicating that the radius of the LnIII ions can regulate the proton conductivity of these MOFs. Additionally, 2 exhibits a significant magnetocaloric effect (MCE) with a magnetic entropy change (-ΔSm) of 18.86 J kg-1 K-1 for ΔH = 7 T at 2 K, and 4 shows weak field-induced slow relaxation of magnetization. The coexistence of good fluorescence sensing capability, attractive proton conductivity, and relatively large MCE in Ln-MOFs is rare, and thus, 1-4 are potentially multifunctional MOF materials.

Field-induced single-molecule magnet behaviour in a series of dinuclear cobalt(III,II) complexes

We present the synthesis, structure and magnetic characterization of four dinuclear cobalt(III,II) complexes: [(NCS)CoIII(Ln)(µ–OAc)CoII(NCS)]·G, with n/G = 1/CH3OH (1), 2/CH3CN (2), 3/- (3) and 4/CH3OH (4), being H2Ln, four closely related reduced Schiff base ligands: H2L1 = (1,3-propanediyl)bis(iminomethylene)bis(6-methoxyphenol), H2L2 = (1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol), H2L3= (2,2-dimethyl-1,3-propanediyl)-bis(iminomethylene)bis(6-methoxyphenol) and H2L4= (2,2-dimethyl-1,3-propanediyl)-bis(iminomethylene)bis(6-ethoxyphenol). The single crystal X-ray structures of complexes 1–4 show that both cobalt centres in the four complexes adopt a distorted octahedral geometry with Co(III) and Co(II) centres residing at inner N2O2 and outer O4 pockets of the reduced Schiff base, respectively. Magnetic measurements show that all complexes behave as Co(II) monomers, confirming the presence of diamagnetic low spin Co(III) ions, which have also been supported by the spin-density calculation using Density Functional Theory. Additionally, complexes 1–4 show a field-induced slow relaxation of the magnetization at low temperatures that follow direct and Raman mechanisms.