Single-ion Magnets Research Articles

Boosting the mono-axial crystal field in stable high-coordinate Dy(III) single-ion magnets by substitution of the phenoxy axial ligand.

Synthesis of air-stable and high-performance single-molecule magnets (SMMs) is challenging. Here, a heptadentate pentapyridyldiamine (BPA-TPA) ligand and fine-tuned axial phenoxy ligands are used to synthesize two triangular dodecahedral Dy(III) complexes [Dy(BPA-TPA)(4-methoxy-PhO)](BPh4)2·3CH2Cl2 (4) and [Dy(BPA-TPA)(2,4-dimethyl-PhO)](BPh4)2·0.85CH2Cl2 (5). Both complexes have high effective barriers exceeding 400 K and magnetic hysteresis up to 8 K, which is ascribed to one strong and short Dy-O bond combined with seven weak Dy-N bonds. Ab initio calculations reveal the thermally activated quantum tunneling of magnetization through the first excited Kramers doublet, due to the presence of a strong axial Dy-O crystal ligand. Substitution of the phenoxy ligand leads to more constrained vibrations, improving the magnetic hysteresis behavior for 5.

A Dy-based single ion magnet in a SrLaGaO4 matrix: enhanced parameters in an expanded crystal lattice.

Dy3+ doped SrLaGaO4 exhibits unusually slow relaxation of magnetization determined by two widely separated excited Kramers doublets with a second remagnetization energy barrier of 223 cm-1. This value considerably exceeds that for analogous Ca(Y,Dy)AlO4 in spite of the apparently enlarged Dy3+ coordination sphere.

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.

Ab initio prediction of key parameters and magneto-structural correlation of tetracoordinated lanthanide single-ion magnets.

Single-molecule magnets (SMMs) have great potential in becoming revolutionary materials for micro-electronic devices. As one type of SMM and holding the performance record, lanthanide single-ion magnets (Ln-SIMs) stand at the forefront of the family. Lowering the coordination number (CN) is an important strategy to improve the performance of Ln-SIMs. Here, we report a theoretical study on a typical group of low-CN Ln-SIMs, i.e., tetracoordinated structures. Our results are consistent with those of experiments and they identify the same three best Ln-SIMs via a concise criterion, i.e., the co-existence of long τQTM and high Ueff. Compared to the record-holding dysprosocenium systems, the best SIMs here possess τQTM values that are shorter by several orders of magnitude and Ueff values that are lower by ∼1000 Kelvin (K). These are important reasons for the fact that the tetracoordinated Ln-SIMs are clearly inferior to dysprosocenium. A simple but intuitive crystal-field analysis leads to several routes to improve the performance of a given Ln-SIM, including compression of the axial bond length, widening the axial bond angle, elongation of the equatorial bond length and usage of weaker equatorial donor ligands. Although these routes are not brand-new, the most efficient option and the degree of improvement resulting from it are not known in advance. Consequently, a theoretical magneto-structural study, covering various routes, is carried out for the best Ln-SIM here and the most efficient route is shown to be widening the axial ∠O-Dy-O angle. The most optimistic case, having a ∠O-Dy-O of 180°, could have a τQTM (up to 103 s) and Ueff (∼2400 K) close to those of the record-holders. Subsequently, a blocking temperature (TB) of 64 K is predicted to be possible for it. A more practical case, with ∠O-Dy-O being 160°, could have a τQTM of up to 400 s, Ueff of around 2200 K and the possibility of a TB of 57 K. Although having an inherent precision limit, these predictions provide a guide to performance improvement, starting from an existing system.

Triggering single-molecule qubit spin dynamics via non-Abelian geometric phase effects.

We illustrate how macroscopic rotations can be utilised to trigger and control a spin dynamics within the ground doublet of both Kramers and non-Kramers-type molecular nanomagnets via the non-Abelian character of the time-evolution operator. For Kramers magnets, we show how this effect can be harnessed to realise single-qubit quantum gates and give the explicit example of a recently reported CoCl2(tu)4 single-molecule magnet (SMM). We demonstrate that gating operations could be performed on this magnet in as fast as 10 ps before the breakdown of adiabaticity, much faster than typical spin-lattice relaxation times. Based on this effect, we also suggest CoCl2(tu)4 as a quantum gyroscope for sensing yaw-axis rotations. For integer spin nanomagnets where non-axial crystal field interactions often lift ground state degeneracy, we show how spin dynamics from the non-Abelian geometric propagator can be recovered using non-adiabatic macroscopic rotations not-necessarily resonant with the tunnel splitting gap. Using the well-known TbPc2 single-ion magnet as a further example, we identify an experimentally plausible non-adiabatic rotation that induces a coherent superposition of tunnelling ground states, tantamount to preparing each member of a TbPc2 ensemble in the maximal angular momentum state |mJ = 6〉. The detection of an ensuing coherent oscillation of the macroscopic magnetisation polarised along the TbPc2 principal magnetic axis after the completed rotation could then proceed via time-resolved magnetisation measurements.

Kink distortion of the pseudo-S4 axis in pseudotetrahedral [N2O2] bis-chelate cobalt(II) single-ion magnets leads to increased magnetic anisotropy.

Two new mononuclear cobalt(II) complexes with the general formula [Co(L1,2)2] (1 and 2) were synthesized using bidentate Schiff base ligands with NO donor set, namely, 2-(benzothiazole-2-ylimino)methyl-5-(diethylamino)phenol (HL1) and its methyl substituted derivative 2-(6-methylbenzothiazole-2-ylimino)methyl-5-(diethylamino)phenol (HL2). X-ray structure analysis reveals a distorted pseudotetrahedral coordination sphere at the cobalt(II) ion, that cannot be described by a simple twisting of the two ligand chelate planes with respect to each other, which would imply a rotation about the pseudo-S4 axis of the complex. Such a pseudo-rotation axis would approximately be colinear with the two vectors defined by the cobalt ion and the two centroids of the chelate ligands, where the angle κ between the two vectors would be 180° in an ideal pseudotetrahedral arrangement. For complexes 1 and 2, the observed distortion can be characterized by a significant bending at the cobalt ion with angles κ of 163.2° and 167.4°, respectively. Magnetic susceptibility and FD-FT THz-EPR measurements together with ab initio calculations reveal an easy-axis type of anisotropy for both complexes 1 and 2, with a spin-reversal barrier of 58.9 and 60.5 cm-1, respectively. For both compounds, frequency-dependent ac susceptibility measurements show an out-of-phase susceptibility under applied static fields of 40 and 100 mT, which can be analyzed in terms of Orbach and Raman processes within the observed temperature range.

Binuclear cobalt(II) and two-dimensional manganese(II) coordination compounds self-assembled by mixed bipyridine-tetracarboxylic ligands with single-ion magnet properties.

A cobalt(II) complex and manganese(II) coordination polymer, formulated as [Co2(H2btca)(mbpy)4][H2btca]·4H2O (1) and {Mn2(btca)(mbpy)2(H2O)2}n (2) (H4btca = 1,2,4,5-benzenetetracarboxylic acid; mbpy = 4,4'-dimethyl-2,2'-bipyridyl), constructed by mixed bipyridine-tetracarboxylic ligands were synthesized and characterized. Single-crystal structural analyses reveal that compound 1 is a discrete neutral binuclear molecule, while compound 2 is a two-dimensional (2D) coordination polymer. The metal ions in these compounds are well isolated, with an intramolecular Co2+⋯Co2+ distance of 9.170 Å for 1 and Mn2+⋯Mn2+ separation of 10.984 and 11.164 Å for 2 due to the bulk tetracarboxylic linker. This isolation gives rise to a single-ion magnetism origin of the compounds. Magnetic studies reveal a large zero-field splitting parameter D of 82.6 cm-1 for 1, while a very small D of 0.42 cm-1 was observed for 2. Interestingly, dynamic ac magnetic measurements exhibited slow magnetic relaxation under the external dc field of the two compounds, revealing the field-supported single-ion magnet (SIM) of 1 and 2. The detailed theoretical calculations were further applied to understand the electronic structures, magnetic anisotropy, and relaxation dynamics in 1 and 2. Combined with our recently reported compound (Eur. J. Inorg. Chem., 2022, e202200354), the foregoing results provide not only a rare binuclear cobalt(II) SIM and the first 2D manganese(II) SIM coordination polymer but also a bipyridine-tetracarboxylic ligand approach toward novel SIMs.

Abnormal magnetic phenomenon at low temperature in Zn doped <inline-formula><tex-math id="M1">\begin{document}$ \left[{(\mathbf{C}\mathbf{H}}_{3}{)}_{2}\mathbf{N}{\mathbf{H}}_{2}\right]{\mathbf{C}\mathbf{o}}_{\mathit{x}}{\mathbf{Z}\mathbf{n}}_{1-\mathit{x}}{\left[\mathbf{H}\mathbf{C}\mathbf{O}\mathbf{O}\right]}_{3} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M1.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M1.png"/></alternatives></inline-formula> frameworks

Metal-organic framework (MOF) is a new type of inorganic-organic hybrid porous material composed of organic ligands bridging metal ions, and it has the characteristics of tunable functions, good stability and porosity. In this study, Zn doped Co-based metal organic frame works single-crystal samples<inline-formula><tex-math id="M2">\begin{document}$\left[{(\rm{C}\rm{H}}_{3}{)}_{2}\rm{N}{\rm{H}}_{2}\right]{\rm{C}\rm{o}}_{1-x}{\rm{Z}\rm{n}}_{x} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M2.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M2.png"/></alternatives></inline-formula><inline-formula><tex-math id="M2-1">\begin{document}$ {\left[\rm{H}\rm{C}\rm{O}\rm{O}\right]}_{3}$\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M2-1.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="3-20221761_M2-1.png"/></alternatives></inline-formula>are synthesized by the solvothermal method with normal ratio <i>x</i> = 0, 0.1, 0.2, 0.3, 0.4, 0.5. Single crystal diffraction, scanning electron microscope and energy dispersive X-ray spectroscopy results show that Zn ions are uniformly doped into Co-based MOFs crystals. The field cooling curves show that antiferromagnetic phase transition temperature of Co-based MOFs decreases from 15 K for pure Co-MOF <i>x</i> = 0 to 12.8 K for <i>x</i> = 0.2. Abnormal large magnetic hysteresis is obtained for Zn doped crystals with large coercive field 3600 Oe (<i>x</i> = 0.3) compared with 450 Oe coercive field for pure Co-MOF (<i>x</i> = 0), and the hysteresis area of Zinc-doped sample is more than 3 times that of pure cobalt sample. On the other hand, we find a series of steps on the hysteresis loop of DMCo<sub>0.9</sub>Zn<sub>0.1</sub>F sample, which gradually disappears with the increase of temperature, similar to the quantum tunneling phenomenon of a single molecule magnet. Previous studies have shown that the long range magnetic interaction and the magnetic single-ion behavior competition coexist in these systems. It is believed that the doping of non-magnetic zinc ions weakens the long-range interaction between Co ions and makes Co ions show the step effect caused by quantum tunneling at low temperature.

A pentagonal bipyramidal Co(II) single-ion magnet based on an asymmetric tetradentate ligand with easy plane anisotropy

High-coordinate 3d single-ion magnets(SIMs) especially with pentagonal bipyramidal geometry as an emerging class of representative molecular magnets have received considerable concern. Whereas, it is not easy to construct and obtain 3d SIMs with high coordination numbers (CN = 7 or 8). Herein, a mononuclear Co(II) complex ([Co(pypzbeyz)(NCS)2(DMF)], pypzbeyz = N-((6-(1H-pyrazol-1-yl)pyridin-2-yl)methylene)benzohydrazide) based on a tetradentate ligand has been synthesized and structurally and magnetically characterized. Single-crystal X-ray diffraction analysis reveals that the Co(II) complex adopts a seven-coordinate distorted pentagonal bipyramidal geometry. Magnetic investigations show that the Co(II) complex has large easy plane anisotropy with a positive D value (D = +36.8 cm−1) and a small E value, and exhibits slow magnetic relaxation behavior under a dc field. Theoretical calculations show a positive zero-field splitting of 33.5 cm−1, which is in excellent agreement with the experiment. The results support that the 3d high-coordinate SIMs could be effectively achieved by using a suitable multi-dentate ligand with a certain ligand field.

A DyIII single-ion magnet with D5h configuration

A DyIII single-ion magnet [Dy(L1)(L2)] (1, HL1 = (E)-2-(((3-aminopropyl)imino)methyl) phenol, H2L2 = 2,2′-((1E,1′E)-(propane-1,3-diylbis(azaneylylidene))bis(methaneylylidene))diphenol) was synthesized by self-assembly of dysprosium nitrate hexahydrate, 1,3‑diaminopropane and salicylaldehyde under solvothermal method. As far as we know, complex 1 synthesized in this work is the highest Ueff of pentagonal bipyramidal with four neutral nitrogen atoms and one oxygen anion occupying the equatorial plane, while the axis is occupied by two oxygen atoms, in DyIII single-molecule magnets. Magnetic characterizations reveal that complex 1 exhibit slow magnetic relaxation behavior with Ueff = 95.98 K and τ0 = 8.76 × 10-7 s.

Axial Ligand as a Critical Factor for High-Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnets.

The choice of axial ligands is of great importance for the construction of high-performance Dy-based single-molecule magnets (SMMs). Here, combining axial ligands Ph3SiO- (anion of triphenylsilanol) and 2,6-dichloro-4-nitro-PhO- (the anion of 2,6-dichloro-4-nitrophenol) with a neutral macrocyclic ligand 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene (L2N5) generates two new pentagonal bipyramidal Dy(III) complexes [DyIII(L2N5) (X)2](BPh4) (X = Ph3SiO-, 1; 2,6-dichloro-4-nitro-PhO-, 2) with strong axial ligand fields. Magnetic characterizations show that 1 possesses a large energy barrier above 1000 K and a magnetic hysteresis up to 9 K, whereas 2 only displays field-induced peaks of alternating-current susceptibilities without the hysteresis loop, even though 2 has a similar coordination geometry with 1. Detailed Ab initio calculations indicate an apparent difference in the axial negative charge between both complexes, which is caused by the diverse electron-donating properties of the axial ligands. The present work provides an efficient strategy to enhance the SMMs' properties, which highlights that the electron-donating property of the axial ligands is especially important for constructing the high-performance Dy-based SMMs.

Single-Ion Magnets with Giant Magnetic Anisotropy and Zero-Field Splitting.

The design of mononuclear molecular nanomagnets exhibiting a huge energy barrier to the reversal of magnetization have seen a surge of interest during the last few decades due to their potential technological applications. More specifically, single-ion magnets are peculiarly attractive by virtue of their rich quantum behavior and distinct fine structure. These are viable candidates for implementation as single-molecule high-density information storage devices and other applications in future quantum technologies. The present review presents the comprehensive state of the art in the topic of single-ion magnets possessing an eminent magnetization-reversal barrier, very slow magnetic relaxation and high blocking temperature. We turn our attention to the achievements in the synthesis of 3d and 4f single-ion magnets during the last two decades and discuss the observed magnetostructural properties underlying the anisotropy behavior and the ensuing remanence. Furthermore, we highlight the fundamental theoretical aspects to shed light on the complex behavior of these nanosized magnetic entities. In particular, we focus on key notions, such as zero-field splitting, anisotropy energy and quantum tunneling of the magnetization and their interdependence.

Efficient Multiconfigurational Quantum Chemistry Approach to Single-Ion Magnets Based on Density Matrix Embedding Theory.

Density matrix embedding theory (DMET) provides a systematic framework to combine low-level (e.g., Hartree-Fock approximation) and high-level correlated quantum chemistry methods to treat strongly correlated systems. In this work, we propose an efficient quantum embedding approach that combines DMET with the complete active space self-consistent field and subsequent state interaction treatment of spin-orbit coupling (CASSI-SO) and apply it to a theoretical description of single-ion magnets (SIMs). We have developed a novel regularized direct inversion of iterative subspace (R-DIIS) technique that ensures restricted open-shell Hartree-Fock converging to a physically correct ground state, which is found to be crucial for the efficacy of subsequent CASSI-SO calculation. The DMET+CASSI-SO approach can produce reliable zero-field splitting parameters in typical 3d-SIMs with dramatically reduced computational cost compared to its all-electron counterpart. This work therefore demonstrates the great potential of DMET-based multiconfigurational approaches for efficient ab initio study of magneto-structural correlations in complex molecular magnetic systems.

Mononuclear Heptacoordinated 3d-Metal Helicates as a New Family of Single Ion Magnets

The series of Co(II), Fe(II), and Ni(II) mononuclear coordination compounds of [CoL(NCS)2]·3DMSO (1), [CoL(H2O)2](ClO4)2·DMSO (2), [CoL(H2O)(EtOH)][CoCl4]·2H2O (2a), [FeL(NCS)2]·DMSO (3), and [NiL(NCS)2]·CH3CN (4) composition (where L is 2,6-bis(1-(2-(4,6-dimethylpyrimidin-2-yl)hydrazineylidene)ethyl)pyridine), with an [MLA2] coordination unit (where A is a pair of apical monodentate ligands), was synthesized. In compounds 1, 2, 2a, and 3, the ligand L is pentadentate, and cobalt and iron ions are placed in a heavily distorted pentagonal pyramidal coordination environment, while in 4 the Ni(II) ion is hexacoordinated. Easy plane-type magnetic anisotropy (D = 13.69, 11.46, 19.5, and 6.2 cm−1 for 1, 2, 2a, and 4, respectively) was established for cobalt and nickel compounds, while easy axis-type magnetic anisotropy (D = −14.5 cm−1) was established for iron compound 3. The cobalt coordination compounds 1 and 2 show SIM behavior under a 1500 Oe external magnetic field, with effective magnetization reversal barriers of 65(1) and 60(1) K for 1 and 2, respectively. The combination of Orbach and Raman relaxation mechanisms was shown to adequately describe the temperature dependence of relaxation times for 1 and 2. CASSCF/NEVPT2 calculations were performed to model the parameters of the effective spin Hamiltonian for the compounds under study.

Field-induced single-ion magnet behavior in a cobalt(II) coordination polymer constructed by a mixed bipyridyl-tetracarboxylate strategy

A porous two-dimensional (2D) cobalt(II) metal–organic framework (MOF), {[Co(H2tbca)(bpb)(H2O)2]·bpb}n (H4tbca = 1,2,4,5-Benzenetetracarboxylic acid; bpb = 1,4-bis(pyrid-4-yl)benzene), was synthesized and structurally characterized. Single crystal X-ray diffraction analysis indicates that the monometallic Co2+ ion acted as coordination nodes in a distorted octahedral geometry and bridged by H2tbca2− and bpb ligands, giving rise to a porous 2D sql network. Thermal analysis reveals high thermal stability of the framework material even losing its guest molecules. Magnetic studies showed that the six-coordinated Co2+ ions exhibit large easy-plane magnetic anisotropy with the zero-field splitting parameter D = 62.1 cm−1. For the presence of significant single-ion magnetic anisotropy, single-ion magnet (SIM) behavior through combined Direct and Raman mechanisms was evidenced with the effective energy Ueff = 31.8 cm−1. The forgoing result provides a new 2D cobalt(II) SIM-MOF and a potential bipyridyl-tetracarboxylate approach for the construction of SIM frameworks.

Synthesis, structure, magnetism and proton conductivity of a cyanide-bridged NiIICoIII framework

A two-dimensional cyanide-bridged NiIICoIII coordination polymer, {[Ni(cyclam)]3[Co(CN)6]2·16H2O}n (1, cyclam = 1,4,8,11-tetraazacyclotetradecane), was constructed from hexacyanidocobaltate(III) anions, cyclam ligands and Ni2+ ions. Single-crystal X-ray structural analysis revealed that the [Ni(cyclam)]2+ species were bridged by [Co(CN)6]3- building units, leading to a 2D honeycomb topological structure. Interestingly, 1D microporous channels within the framework were formed with guest water molecules located. An N2 adsorption experiment supports the porosity of the compound. Magnetic investigations reveal the easy-axis magnetic anisotropy of the distorted octahedral Ni2+ ions in 1. However, no single-ion magnet behavior was observed. Due to the presence of significant hydrogen-bonded water channels, temperature- and humidity-dependent proton conduction behavior was observed in 1. The electrical conductivity reaches 2.9 × 10−4 S cm−1 at 44 °C and 100 % relative humidity. The forgoing results provide a relatively rare porous cyanide-bridged magnetic framework with proton conduction behavior. Additionally, this compound also highlights that cyanide-bridged frameworks are a potential great platform for the development of high-performance proton-conducting materials.

A Pair of Chiral Dysprosium Single-Ion Magnets with 2,6-Bis[(4S/4R)4-phenyl-2-oxazolinyl]pyridine and Hexafluoroacetylacetonate Ligands

A Pair of Chiral Dysprosium Single-Ion Magnets with 2,6-Bis[(4S/4R)4-phenyl-2-oxazolinyl]pyridine and Hexafluoroacetylacetonate Ligands

Single-Molecule Magnetism in Linear Fe(I) Complexes with Aufbau and Non-Aufbau Ground States.

With the ongoing efforts on synthesizing mononuclear single-ion magnets (SIMs) with promising applications in high-density data storage and spintronics devices, the linear or quasi-linear Fe(I) complexes emerge as the enticing candidates possessing large unquenched angular momentum. Herein, we have studied five experimentally synthesized linear Fe(I) complexes to uncover the origin of single-molecule magnetic behavior of these complexes. To begin with, we benchmarked the methodology on the experimentally and theoretically well-studied complex [Fe(C(SiMe3)3)2]-1 (1) (SiMe3 = trimethylsilyl), which is characterized with a large spin-reversal barrier of 226 cm-1. Subsequently, the spin-phonon coupling coefficients are calculated for the low-frequency vibrational modes to understand the relaxation mechanism of the complex. Furthermore, the two Fe(I) complexes, that is, [Fe(cyIDep)2]+1 (2) (cyIDep = 1,3-bis(2',6'-diethylphenyl)-4,5-(CH2)4-imidazole-2-ylidene) and [Fe(sIDep)2]+1 (3) (sIDep = 1,3-bis(2',6'-diethylphenyl)-imidazolin-2-ylidene), are studied that are experimentally reported with no SIM behavior under ac or dc magnetic fields; however, they exhibit large opposite axial zero field splitting (-62.4 and +34.0 cm-1, respectively) from ab initio calculations. We have unwrapped the origin of this contrasting observation between experiment and theory by probing their magnetic relaxation pathways and the pattern of d orbital splitting. Additionally, the two experimentally synthesized Fe(I) complexes, that is, [(η6-C6H6)FeAr*-3,5-Pr2i] (4) (Ar*-3,5-Pr2i = C6H-2,6-(C6H2-2,4,6-Pr3i)2-3,5-Pr2i) and [(CAAC)2Fe]+1 (5) (CAAC = cyclic (alkyl) (amino)carbene), are investigated for SIM behavior, since there is no report on their magnetic anisotropy. To this end, complex 4 presents itself as the possible candidate for SIM.

The Role of the Bridge in Single-Ion Magnet Behaviour: Reinvestigation of Cobalt(II) Succinate and Fumarate Coordination Polymers with Nicotinamide

Two previously synthesized cobalt(II) coordination polymers; {[Co(μ2-suc)(nia)2(H2O)2]·2H2O}n (suc = succinate(2−), nia = nicotinamide) and [Co(μ2-fum)(nia)2(H2O)2]n (fum = fumarate(2−)) were prepared and thoroughly characterized. Both complexes form 1D coordination chains by bonding of Co(nia)2(H2O)2 units through succinate or fumarate ligands while these chains are further linked through hydrogen bonds to 3D supramolecular networks. The intermolecular interactions of both complexes are quantified using Hirshfeld surface analysis and their infrared spectra, electronic spectra and static magnetic properties are confronted with DFT and state-of-the-art ab-initio calculations. Dynamic magnetic measurements show that both complexes exhibit single-ion magnet behaviour induced by a magnetic field. Since they possess very similar chemical structure, differing only in the rigidity of the bridge between the magnetic centres, this chemical feature is put into context with changes in their magnetic relaxation.

Ferromagnetic Coupling and Single-Ion Magnet Phenomenon in Mononuclear Ruthenium(III) Complexes Based on Guanine Nucleobase

Two mononuclear RuIII complexes of formula trans-[RuCl4(Hgua)(dmso)]·2H2O (1) and trans-[RuCl4(Hgua)(gua)]·3H2O (2) [Hgua = protonated guanine (gua), dmso = dimethyl sulfoxide] have been synthesized and characterized magnetostructurally. 1 and 2 crystallize in the monoclinic system with space groups P21/n and Pc, respectively. Each RuIII ion in 1 and 2 is bonded to four chloride ions and one (1) or two (2) nitrogen atoms from guanine molecules and one sulfur atom (1) of a dmso solvent molecule, generating axially compressed octahedral geometries in both cases. In their crystal packing, the RuIII complexes are connected through an extended network of N-H⋯Cl hydrogen bonds and π⋯Cl intermolecular interactions, forming novel supramolecular structures of this paramagnetic 4d ion. Variable-temperature dc magnetic susceptibility data were obtained from polycrystalline samples of 1 and 2 and their plots show a different magnetic behavior. While 1 is a ferromagnetic compound at low temperature, 2 exhibits a behavior of magnetically isolated mononuclear RuIII complexes with S = 1/2. The study on ac magnetic susceptibility data reveal slow relaxation of the magnetization, when external dc fields are applied, only for 2. These results highlight the presence of field-induced single-ion magnet (SIM) behavior for this mononuclear guanine-based RuIII complex.