Intermolecular Magnetic Interactions Research Articles

Aggregation‐induced suppression of quantum tunneling by manipulating intermolecular arrangements of magnetic dipoles

AbstractThe relaxation time under zero field reflects the memory retention capabilities of single‐molecule magnets (SMMs) when used as storage devices. Intermolecular magnetic dipole interaction is ubiquitous in aggregates of magnetic molecules and can greatly influence relaxation times. However, such interaction is often considered harmful and challenging to manipulate in molecular solids, especially for high‐performance lanthanide single‐ion magnets (SIMs). By an elaborately designed combination of ion pairing and hydrogen bonding, we have synthesized two pseudo‐D5h SIMs with supramolecular arrangements of magnetic dipoles in staggered and side‐by‐side patterns, the latter of which exhibits a 104‐fold slower zero‐field relaxation time at 2 K. Intriguingly, the side‐by‐side complex exhibits a significantly accelerated magnetic relaxation upon diamagnetic dilution, contrary to the general trend observed in the staggered complex. This strongly reveals the presence of aggregation‐induced suppression of quantum tunneling in a side‐by‐side arrangement, which has not been observed in mononuclear SMMs. By leveraging ion‐pairing aggregation and converting to a side‐by‐side pattern, this study successfully demonstrates an approach to transform a harmful intermolecular dipole interaction into a beneficial one, achieving a τQTM of 980 s ranking among the best‐performance SMMs.

Photoresponsive Magnetic Relaxation Behavior of a Highly Stable π···π Interaction-Stacked Framework Based on a DyIII Single-Ion Magnet

Endowing lanthanide single-ion magnets (Ln-SIMs) with high stability and stimulus responsiveness is of significance for the practical applications of these novel magnetic materials, but still of challenge at present. Herein, we report on a highly stable and photoresponsive Ln-SIM system achieved by designing and synthesizing a π···π interaction-stacked framework based on DyIII-SIM (πOF-1). Its molecular formula is [Dy(thqa)] (H3thqa = tris[(8-hydroxyquinoline-2-yl)methylene]amino). Each of its C3-symmetric molecules consists of a thqa3– ligand and a DyIII ion, and it is linked to three neighbors by intermolecular π···π interactions, forming a supermolecular two-dimensional (2D) honeycombed topology. Such unique structure endows πOF-1 with not only air and thermal stability but also excellent chemical stability in different solvents, even in alkali solutions, including a 20 M NaOH aqueous solution. Dual magnetic relaxation behavior was observed in πOF-1. Magnetic dilution revealed that it is related to π···π-mediated intermolecular magnetic interactions. More significantly, both the static magnetic susceptibility and the dual-relaxation behavior of πOF-1 show response to photoirradiation, which could be ascribed to the photo-triggered intermolecular π → π* charge transfer (CT). So far as we know, πOF-1 could be the first Ln-SIM system possessing both a high stability and photoresponsiveness, and also the first photoresponsive Ln-SIM supermolecular system that does not rely on the single-crystal to single-crystal (SCSC) structural transformation. Its successful design and synthesis suggests that the introduction of π···π interactions can be a new strategy to fabricate stable and/or photoresponsive Ln-SIMs.

Air-Stable Dy(III)-Macrocycle Enantiomers: From Chiral to Polar Space Group

Air-Stable Dy(III)-Macrocycle Enantiomers: From Chiral to Polar Space Group

Front Cover: Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety (ChemPlusChem 3/2022)

The front cover displays novel ionic liquid crystalline (ILC) compounds containing a nitroxide radical unit in the organic cations, showing an enantiotropic smectic A (SmA) phase. One of the ILC compounds shows strong intermolecular magnetic interactions owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. Its droplet can be magnetically manipulable. More information can be found in the Full Paper by Yoshiaki Uchida, Rui Tamura, and co-workers.

Exact classical spin dynamics of high spin nanoscale molecular magnetic clusters

A common feature of many organic-based molecular magnets is that inter-molecular magnetic interactions are extremely weak compared to intra-molecular ones. As a result a bulk sample can be described in terms of independent individual molecular magnets made up of a cluster of a small finite number of coupled magnetic spins. Because of the large value of individual spins of several molecular magnetic compounds it turns out that such systems can be described to very high accuracy, at sufficiently high temperatures, by a classical Heisenberg spin model. Only for sufficiently low temperatures need one incorporate the quantum character of the spins. In this work we focus on the exact classical spin dynamics of small nanoscale molecular magnetic clusters of classical Heisenberg spins. The present study permits us to obtain analytical solutions for the time-dependent spin-spin autocorrelation function for certain clusters of classical Heisenberg spins coupled through exchange interaction. This study underscores the potential utility of a classical spin treatment of nanoscale magnetic clusters and provides results useful to interpret data obtained from experiments.

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety.

With a view to fabricating a new remote input-output system by applying functional ionic liquid crystalline (ILC) materials, we have developed novel ILC compounds containing a nitroxide radical unit in the organic cations, which show an enantiotropic smectic A (SmA) phase. We have implemented the magnetic manipulation of a droplet of one of the ILC compounds on the basis of the intermolecular magnetic interactions between radical moieties. This ILC monoradical compound shows a 55 % larger increase in paramagnetic susceptibility at the solid-to-LC melting point in the first heating process than the non-ionic LC monoradical compounds. It is most likely owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. The increased molar magnetic susceptibility is preserved not only in the SmA phase but also in the isotropic liquid and solid phases during the first cooling process.

A quasilinear hydrazone-based mononuclear dysprosium compound withC4vsymmetry exhibiting field-induced complex magnetic relaxation

AC4vsymmetrical mononuclear dysprosium(iii) compound has been successfully isolated using a new quasilinear single pyrazinyl hydrazone ligand. Single-ion behavior and the short-range intermolecular magnetic dipolar interaction are essential to the complex magnetic relaxation.

Elucidating the Electronic Structure and Magnetic and Conducting Properties of μ-Oxo Mn-phthalocyanine [MnPc(CN)]2O Complex

The μ-oxo phthalocyanine dimer complex [Mn(Pc)(CN)]2O has been characterized as the first single-component molecular conductor exhibiting magnetoresistance at room temperature. Herewith, we report a detailed study of the electronic structure and the magnetic and conducting properties of this μ-oxo MnPc dimer complex. A combined strategy of wave-function-based quantum chemistry calculations on the complex and plane-wave-based periodic calculations on the crystal has been employed together with semiclassical Boltzmann transport theory calculations. Our results provide information about the ligand field parameters of the Mn ions, clarify their spin states on the [Mn(Pc)(CN)]2O complex, and explain the temperature dependence of both the magnetic susceptibility and the effective magnetic moment, taking into account the presence of excited low-lying states with S = 2 and weak intermolecular magnetic interactions, as key ingredients of the magnetic behavior. The analysis of the density of states of the low-spin and high-spin density functional theory + U magnetic solutions and their respective temperature dependence of the electric resistivity give some clues about the conducting properties and the negative magnetoresistance reported for this system.

Photomagnetic effects in metal-free liquid crystals

Metal-free liquid-crystalline (LC) materials consisting of a LC nitroxide radical compound exhibit light-induced reversible switching of the magnetic properties as a new photomagnetic effect. This behavior is based on the abrupt change of magnetic properties at the phase transition directly from a chiral smectic C phase to an isotropic liquid (Iso) phase. The origin of the abrupt change is probably the difference in the inhomogeneity of the intermolecular magnetic interactions between LC and Iso phases. To our knowledge, there are no existing reports on a material showing the reversible and quick phase transitions with the large difference of the inhomogeneity. Here we show a relatively simple way to design a compound to enlarge the difference between LC and Iso phases and to make the response quick and reversible. In addition, the presented analysis method that mines Gaussian components from electron paramagnetic resonance spectra enables us to precisely evaluate magnetic properties in condensed phases.

Transition metal coordination complexes based on V-shaped bis-triazole ligand: syntheses, structures, and properties

Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO3)2 (M = Co2+ (1), Cu2+ (2)) afforded two new coordination polymers, [Co(btb)2(NO3)(H2O)]n·NO3·H2O (1) and [Cu(btb)2(NO3)2]n (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in the space group P21/m and 2 crystallizes in the space group Pī, both showing a double-stranded chain structure. The 1-D chains are interconnected via π⋯π interactions to lead to 2-D ladder-like supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2 have been investigated. For 1, weak antiferromagnetic interactions are observed at low temperature, and the data obey the Curie–Weiss law χM = C/(T−θ), with C = 3.22 cm3·mol−1·K and θ = −10.39 K. For 2, the decrease of the χT vs. T curve at low temperature is the result of intermolecular antiferromagnetic magnetic interactions.

Insights into Magnetic Interactions in a Monodisperse Gd12 Fe14 Metal Cluster.

The largest Ln-Fe metal cluster [Gd12 Fe14 (μ3 -OH)12 (μ4 -OH)6 (μ4 -O)12 (TEOA)6 (CH3 COO)16 (H2 O)8 ]⋅(CH3 COO)2 (CH3 CN)2 ⋅(H2 O)20 (1) and the core-shell monodisperse metal cluster of 1 a@SiO2 (1 a=[Gd12 Fe14 (μ3 -OH)12 (μ4 -OH)6 (μ4 -O)12 (TEOA)6 (CH3 COO)16 (H2 O)8 ]2+ ) were prepared. Experimental and theoretical studies on the magnetic properties of 1 and 1 a@SiO2 reveal that encapsulation of one cluster into one silica nanosphere not only effectively decreases intermolecular magnetic interactions but also significantly increases the zero-field splitting effect of the outer layer Fe3+ ions.

Cooperative Magnetism in Crystalline N-Aryl-Substituted Verdazyl Radicals: First-Principles Predictions and Experimental Results.

We report on a series of eight diaryl-6-oxo-verdazyl radicals containing a tert-butyl group at the C(3) position with regard to their crystal structure and magnetic properties by means of magnetic susceptibility measurements in combination with quantum chemical calculations using a first-principles bottom-up approach. The latter method allows for a qualitative prediction and detailed analysis of the correlation between the solid-state architecture and magnetic properties. Although the perturbation in the molecular structure by varying the substituent on the N-aryl ring may appear small, the effects upon the structural parameters controlling intermolecular magnetic coupling interactions are strong, resulting in a wide spectrum of cooperative magnetic behavior. The non-substituted 1,5-diphenyl-tert-butyl-6-oxo-verdazyl radical features a ferromagnetic one-dimensional spin ladder type magnetic network-an extremely rarely observed phenomenon for verdazyl radicals. By varying substituents at the phenyl group, different non-isostructural compounds were obtained with widely different magnetic motifs ranging from linear and zigzag one-dimensional chains to potentially two-dimensional networks, from which we predict magnetic susceptibility data that are in qualitative agreement with experiments and reveal a large sensitivity to packing effects of the molecules. The present study advances the fundamental understanding between solid-state structure and magnetism in organically based radical systems.

Preparation and magnetic properties of nitroxide radical liquid crystalline physical gels

ABSTRACTLiquid crystalline physical gels which consist of a chiral racemic nitroxide radical compound (±)-1 showing a nematic phase and a diamagnetic, chiral organic gelator (R,R)-2 were prepared to investigate the effects of the gelator on the “positive magneto-LC effects” observed in the nematic phase of (±)-1 and the molecular alignment of (±)-1 in the resulting nematic gels. With the increasing amount of the gelator which decreased the domain size, the molecular reorientation by a magnetic field (0.34 T) was considerably restricted in the nematic gel phase and the intermolecular magnetic interactions (positive magneto-LC effects) increased in the fine and random nematic polydomain structure formed by self-assembled fibers of organic gelator molecules.

Magnetic properties of terminal iodinated nitroxide radical liquid crystals

We designed and synthesized terminal iodinated nitroxide radical liquid crystalline compounds (NR-LCs) with octyloxy side chain (±)-8-I and dodecyloxy side chain (±)-12-I to understand the substitution effects of an iodine atom on the phase transition behavior and on the magnetic properties in crystalline (Cr), liquid crystalline (LC) and isotropic (Iso) phases. These NR-LCs show monotropic nematic phases because the iodine atom is too short and apolar as a terminal group to stabilize LC phases. Furthermore, the SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy indicate that the magnetic properties in the Cr phase depend on the length of the alkoxy side chain; antiferromagnetic interactions occur in (±)-8-I, whereas ferromagnetic interactions occur in (±)-12-I, and the paramagnetic susceptibility of (±)-8-I slightly decreases (J¯<0) and that of (±)-12-I abruptly increases (J¯>0) at each of the Cr-to-Iso phase transitions. These results suggest that the most frequent type of the magnetic interactions in LC and Iso phases is similar to those in the Cr phases among the various types of intermolecular magnetic interactions induced by the inhomogeneous intermolecular contacts.

Hexahalorhenate(iv) salts of metal oxazolidine nitroxides.

Eight coordination compounds of formulae [FeII(L˙)2][ReIVCl6] (1a), [FeII(L˙)2][ReIVBr6] (1b), [CoII(L˙)2][ReIVCl6]·CH3CN (2a), [CoII(L˙)2][ReIVBr6] (2b), [NiII(L˙)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L˙)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L˙)2][ReIVCl6] (4a) and [CuII(L˙)2][ReIVBr6] (4b), where L˙ is the aminoxyl radical chelating ligand, 4,4'-dimethyl-2,2'-di(2-pyridyl)oxazolidine-N-oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L˙)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of iron (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggest that the dried samples are best formulated as [NiII(L˙)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms of 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc = 580 Oe, and a remanent magnetisation Mr = 0.21μB, resulting in a canting angle of ∼1.8°. In contrast, 3b(dried) shows no spin-canting behaviour; a maximum in χMvs. T at T = 3 K suggesting long-range antiferromagnetic ordering. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.

Slow relaxation dynamics of a mononuclear Er(iii) complex surrounded by a ligand environment with anisotropic charge density.

Two sets of isostructural mononuclear compounds, [Ln(LOMe)2(H2O)2](PF6) [1, Ln = Er; 3, Ln = Gd; LOMe = CpCo{P(O)(O(CH3))2}3] and Ln(LOMe)2(NO3) (2, Ln = Er and 4, Ln = Gd), are synthesized by self-assembly of the respective lanthanide ions and tripodal chelate ligands. The Ln ions are encircled by two LOMe ligands, and two water molecules or one nitrate anion. Each octacoordinated Ln center adopts a distorted square antiprism geometry. The Er complex (2) chelated by a nitrate anion shows slow dynamics in magnetic relaxation, diagnostic of a single-ion magnet. Quantum tunneling in 2 is effectively blocked by application of an external field. Weak intermolecular magnetic interactions occur in 2, and are supported by the magnetic behavior of 4. Chemical dilution of Er with the diamagnetic Y ion can nullify magnetic interactions and suppress quantum tunneling. Generation of slow relaxation dynamics in the Er system is related to the anisotropic charge distribution supplied by the coordination of ligands with different charge densities, as observed in the Dy analogue. This suggests that magnetic anisotropy arises in a coordination system when an anisotropic lanthanide ion (Dy and Er) is surrounded by a ligand environment with anisotropic charge density, resulting in slow magnetic relaxation.

Hexaethyltripyrrindione (H3Et6tpd): A Non‐Innocent Ligand Forming Stable Radical Complexes with Divalent Transition‐Metal Ions

Nickel, palladium, and copper complexes of the tripyrrolic ligand hexaethyltripyrrindione (H3Et6tpd, 1) have been prepared and characterized by UV/Vis and EPR spectroscopy, as well as by single‐crystal X‐ray structure determination. In all cases the metal ion is coordinated in a distorted square‐planar geometry carrying a water ligand at the fourth coordination site. The Et6tpd ligand acts as a radical dianion in all cases. In solution, monomeric species are present in which the open‐shell character of the ligand becomes apparent through EPR spectroscopic measurements. In the solid state, the compounds form polymorphs with tightly bonded π–π dimers and chains showing small interplanar distances of 3.191–3.493 Å to one or more neighboring molecules. Magnetic measurements on the complexes confirmed the radical character of the tripyrrindione ligand and revealed strong intermolecular magnetic interactions in these complexes.

A Stable Organic π-Radical of a Zinc(II)-Copper(I)-Zinc(II) Complex of Decaphyrin.

A Zn(II) -Cu(I) -Zn(II) heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a [46]decaphyrin with Zn(II) ions to produce a 46π decaphyrin bis(Zn(II) ) complex and its subsequent metalation with Cu(II) ion. In the second metalation step, it has been shown that Cu(II) ion is reduced to a Cu(I) ion in the complex and a dianionic bis(Zn(II) ) containing [46]decaphyrin ligand is oxidized to the corresponding monoanionic [45]decaphyrin ligand, indicating a non-innocent nature of the decaphyrin ligand. Despite the radical nature, the heterotrimetal complex is fairly stable under ambient conditions and exhibits almost no intermolecular magnetic interaction, owing to extensive delocalization of an unpaired electron in the large π-conjugated circuit of decaphyrin moiety.

A Stable Organic π‐Radical of a Zinc(II)–Copper(I)–Zinc(II) Complex of Decaphyrin

AbstractA ZnII‐CuI‐ZnII heterotrimetal complex of decaphyrin was synthesized by stepwise metalations: metalation of a [46]decaphyrin with ZnII ions to produce a 46π decaphyrin bis(ZnII) complex and its subsequent metalation with CuII ion. In the second metalation step, it has been shown that CuII ion is reduced to a CuI ion in the complex and a dianionic bis(ZnII) containing [46]decaphyrin ligand is oxidized to the corresponding monoanionic [45]decaphyrin ligand, indicating a non‐innocent nature of the decaphyrin ligand. Despite the radical nature, the heterotrimetal complex is fairly stable under ambient conditions and exhibits almost no intermolecular magnetic interaction, owing to extensive delocalization of an unpaired electron in the large π‐conjugated circuit of decaphyrin moiety.

Purely organic magnets: How to get ferromagnetic interactions

Purely organic magnets, materials with spontaneous magnetization despite no containing magnetic ions, are very promising for technological applications due to their peculiar properties as flexibility, lightness or even biocompatibility. Most of the published purely organic magnets are free radical compounds. One of the most important difficulties in order to get spontaneous magnetization in such materials is that magnetic interactions among free radicals are usually antiferromagnetic and, in addition, ferromagnetic interactions are weaker than the antiferromagnetic ones. A possible strategy to overcome this issue is the use of triradical molecules with total spin S=1/2. In this case, an adequate packing of the triradical molecules can give place to antiferromagnetic interactions between regions with positive spin density and regions with negative spin density of two close molecules. This antiferromagnetic interaction between regions with opposite spin density would result in an overall ferromagnetic interaction between the two close triradicals. With this idea in mind we have performed an study of the spin density distribution and of the intramolecular and intermolecular magnetic interactions of the triradical compound 2-[3',5'-bis(Ntert-butylaminoxyl)phenyl]-4,4,5,5-tetramethyl-4,5-dihydro-1-Himidazol-1-oxyl-3-oxide, containing two N-tert-butyl aminoxyls and a nitronyl nitroxide groups. Combination of experimental data from a polarized neutron diffraction experiment and ab initio calculations (DFT) has allowed us to obtain the spin density distribution. In addition, the intramolecular and intermolecular magnetic interactions have been computed by ab initio quantum chemistry methods. The values for the intramolecular interactions confirm the S=1/2 ground state of the triradical. As for the intermolecular interactions, the two strongest ones are ferromagnetic, what is in agreement with the overlapping of regions with opposite spin density of the two interacting triradicals. These results support the strategy of using triradical molecules for obtaining purely organic magnets with higher magnetic transition ordering temperatures since is easier to obtain ferromagnetic interactions between the radicals and these interactions, having an antiferromagnetic origin, can be stronger than typical ferromagnetic interactions between radicals.