Spatially Resolving Electron Spin Resonance of π-Radical in Single-molecule Magnet.

The spintronic properties of magnetic molecules have attracted significant scientific attention. Special emphasis has been placed on the qubit for quantum information processing. The single-molecule magnet bis(phthalocyaninato (Pc)) Tb(III) (TbPc2) is one of the best examined cases in which the delocalized π-radical electron spin of the Pc ligand plays the key role in reading and intermediating the localized Tb spin qubits. We utilized the electron spin resonance (ESR) technique implemented on a scanning tunneling microscope (STM) and use it to measure local the ESR of a single TbPc2 molecule decoupled from the Cu(100) substrate by a two-monolayer NaCl film to identify the π-radical spin. We detected the ESR signal at the ligand positions under the resonance condition expected for an S = 1/2 spin. The results reveal that the π-radical electron is delocalized within the ligands and exhibits intramolecular coupling susceptible to the chemical environment.

Control of the Magnetic Interaction between Single-Molecule Magnet TbPc2 and Superconductor NbSe2 Surface by an Intercalated Co Atom.

We demonstrate that an intercalated Co atom in superconductor NbSe2 could control the magnetic interaction between the adsorbed magnetic molecule of TbPc2 and the NbSe2 substrate. An intercalated Co atom enhances the magnetic interaction between the NbSe2 and the TbPc2 spin to cause Kondo resonance at the TbPc2 position, a spin-singlet state formed by the itinerary electron. By applying a surface-normal magnetic field, we change the molecule's spin direction from the initial one directed to the Co atom to the surface normal. The change appears as a split Kondo resonance at the TbPc2, one of which is enhanced at the Tb site, which disappears when the outer magnetic field normal to the surface is applied and never appears, even if we return B to 0 T. The phenomenon suggests that the intercalated magnetic atoms can control the magnetic interaction between a magnetic molecule and the superconductor NbSe2.

The Japanese Epidemiologic Study for Perioperative Anaphylaxis, a prospective nationwide study: allergen exposure, epidemiology, and diagnosis of anaphylaxis during general anaesthesia.

BACKGROUND: Diagnosis of perioperative anaphylaxis is often challenging. This study describes the utility of a newly developed tool for identifying patients with a high possibility of anaphylaxis, and aimed to investigate the frequency of anaphylaxis with each drug during the perioperative period in Japan. METHODS: This study included patients with anaphylaxis of Grade 2 or higher severity during general anaesthesia at 42 facilities across Japan in 2019 and 2020. We developed and adopted a unique objective evaluation tool yielding a composite score for diagnosing anaphylaxis, which includes the results of skin tests and basophil activation tests, and clinical scores for perioperative anaphylaxis. The number of cases using each drug and the total number of anaphylaxis cases were investigated to calculate the frequency of anaphylaxis. RESULTS: General anaesthesia was performed in 218 936 cases, which included 55 patients with suspected perioperative anaphylaxis. The developed composite score diagnosed 43 of them with a high probability of anaphylaxis. The causative agent was identified in 32 cases. Plasma histamine levels showed high diagnostic accuracy for anaphylaxis. The top causative agents were rocuronium (10 cases in 210 852 patients, 0.005%), sugammadex (7 cases in 150 629 patients, 0.005%), and cefazolin (7 cases in 106 005 patients, 0.007%). CONCLUSIONS: We developed a composite tool to diagnose anaphylaxis, and found that the combination of tryptase levels, skin testing, and basophil activation testing results and clinical score improved the certainty of anaphylaxis diagnosis. The incidence of perioperative anaphylaxis in our study was 1 in about 5000 general anaesthesia cases. CLINICAL TRIAL REGISTRATION: UMIN000035350.

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications.

The unique properties of natural tetrapyrrolic compounds have inspired the rapid growth of research interest in the design and synthesis of artificial porphyrinoids and their metal complexes as a basis of modern functional materials. A special role in the design of such materials is played by sandwich complexes formed by tetrapyrrolic macrocycles with rare earth elements, especially lanthanides. The development of synthetic approaches to the functionalization of tetrapyrrolic compounds and their rare earth complexes has facilitated the intensive development of new applications over the last decade. As a way of expanding the functionalities of rare earth complexes, sophisticated examples have been obtained, including mixed-ligand complexes, π-extended analogues, covalently linked and fused sandwiches, complexes with less-common tetrapyrrols, sandwiches with non-tetrapyrrolic macrocycles and even complexes containing up to six stacked ligands. This review intends to offer a general overview of the preparation of such sophisticated REE tetrapyrrolic sandwiches over the last decade as well as emphasizes the current challenges and perspectives of their application in areas such as single-molecule magnetism (SMM), organic field-effect transistors (OFET), conductive materials and nonlinear optics (NLO).

Electro-Conductive Single-Molecule Magnet Composed of a Dysprosium(III)-Phthalocyaninato Double-Decker Complex with Magnetoresistance.

A one-dimensional (1D) arrangement of an unsubstituted partially oxidized Dy3+ double-decker complex, [DyPc2 ]Ix (Pc=phthalocyaninato, I=iodide; 1.93

Manipulation of the Coordination Geometry along the C4 Rotation Axis in a Dinuclear Tb3+ Triple-Decker Complex via a Supramolecular Approach.

A supramolecular complex (1⋅C60 ) was prepared by assembling (C60-Ih)[5,6]fullerene (C60 ) with the dinuclear Tb3+ triple-decker complex [(TPP)Tb(Pc)Tb(TPP)] (1: Tb3+ =trivalent terbium ion, Pc2- =phthalocyaninato, TPP2- =tetraphenylporphyrinato) with quasi-D4h symmetry to investigate the relationship between the coordination symmetry and single-molecule magnet (SMM) properties. Tb3+ -Pc triple-decker complexes (Tb2 Pc3 ) have an important advantage over Tb3+ -Pc double-decker complexes (TbPc2 ) since the magnetic relaxation processes correspond to the Zeeman splitting when there are two 4f spin systems. The two Tb3+ sites of 1 are equivalent, and the twist angle (φ) was determined to be 3.62°. On the other hand, the two Tb3+ sites of 1⋅C60 are not equivalent. The φ values for sites Tb1 and Tb2 were determined to be 3.67° and 33.8°, respectively, due to a change in the coordination symmetry of 1 upon association with C60 . At 1.8 K, 1 and 1⋅C60 undergo different magnetic relaxations, and the changes in the ground state affect the spin dynamics. Although 1 and 1⋅C60 relax via QTM in a zero applied magnetic field (H), H dependencies of the magnetic relaxation times (τ) for H>1500 Oe are similar. On the other hand, for H<1500 Oe, the τ values have different behaviors since the off-diagonal terms ( B k q ; q ≠ 0 ) affect the magnetic relaxation mechanism. From temperature (T) and H dependences of τ, spin-phonon interactions along with direct and Raman mechanisms explain the spin dynamics. We believe that a supramolecular method can be used to control the magnetic anisotropy along the C4 rotation axis and the spin dynamic properties in dinuclear Ln3+ -Pc multiple-decker complexes.

Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy.

Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic 1 H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charged quadruple and quintuple-decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single-molecule magnet properties, which are controlled by the multi-step redox induced structural changes.

Coexistence of Spin-Lattice Relaxation and Phonon-Bottleneck Processes in GdIII -Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions.

Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+ -phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+ -Gd3+ interactions and the other does not. It was found that the Gd3+ -Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin-lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.

Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7',8,8'-Tetracyano-p-quinodimethane.

Invited for the cover of this issue are Ryuta Ishikawa and Satoshi Kawata at Fukuoka University and co-workers at Osaka University, Tohoku University, and Kumamoto University, Japan, collaborating within the research project "SOFT CRYSTALS". The image depicts the thermally induced simultaneous switching of magnetism and electrical conductivity in a two-dimensional supramolecular architecture composed of dinuclear FeII spin-crossover complexes and partially charged 7,7',8,8'-tetracyano-p-quinodimethanide radicals. 10.1002/chem.201903934.

Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7',8,8'-Tetracyano-p-quinodimethane.

The reaction of Fe(OAc)2 and Hbpypz with neutral TCNQ results in the formation of [Fe2 (bpypz)2 (TCNQ)2 ](TCNQ)2 (1), in which Hbpypz=3,5-bis(2-pyridyl)pyrazole and TCNQ=7,7',8,8'-tetracyano-p-quinodimethane. Crystal packing of 1 with uncoordinated TCNQ and π-π stacking of bpypz- ligands produces an extended two-dimensional supramolecular coordination assembly. Temperature dependence of the dc magnetic susceptibility and heat capacity measurements indicate that 1 undergoes an abrupt spin crossover (SCO) with thermal spin transition temperatures of 339 and 337 K for the heating and cooling modes, respectively, resulting in a thermal hysteresis of 2 K. Remarkably, the temperature dependence of dc electrical transport exhibits a transition that coincides with thermal SCO, demonstrating the thermally induced magnetic and electrical bistability of 1, strongly correlating magnetism with electrical conductivity. This outstanding feature leads to thermally induced simultaneous switching of magnetism and electrical conductivity and a magnetoresistance effect.

Detailed Analysis of the Crystal Structures and Magnetic Properties of a Dysprosium(III) Phthalocyaninato Sextuple-Decker Complex: Weak f-f Interactions Suppress Magnetic Relaxation.

In the research field of single-molecule magnets (SMMs), lanthanoid-lanthanoid interactions, so-called f-f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f-f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII -CdII -phthalocyaninato sextuple-decker complex (Dy2 Cd3 ) reveals that the intramolecular Dy-Dy length in Dy2 Cd3 is more than 13 Å, which is longer than the intermolecular Dy-Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole-dipole interactions are observed in Dy2 Cd3 . From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2 Cd3 is partially suppressed owing to the existence of very weak Dy-Dy interactions. Our results show that even very weak Dy-Dy interactions act as a dipolar bias, suppressing QTM.

DySc2N@C80 Single-Molecule Magnetic Metallofullerene Encapsulated in a Single-Walled Carbon Nanotube.

DySc2N@C80 is an endohedral metallofullerene showing single-molecule magnet (SMM) behavior. In this work, we encapsulated DySc2N@C80-SMMs into the internal one-dimensional nanospace of single-walled carbon nanotubes (SWCNTs). Using transmission electron microscopy, "peapod" structures were clearly observed. From magnetic field dependent measurements, DySc2N@C80 showed stepwise hysteresis characteristic of SMMs even inside the SWCNTs, and the coercivity increased from 0.5 to 4 kOe. In addition, it showed slow relaxation of the magnetization without an applied external magnetic field. This system is the first example where SMMs have been encapsulated in SWCNTs, and this system could be used in future molecular-spintronics devices.

Comparison of the Magnetic Anisotropy and Spin Relaxation Phenomenon of Dinuclear Terbium(III) Phthalocyaninato Single-Molecule Magnets Using the Geometric Spin Arrangement.

Herein we report the synthesis and characterization of a dinuclear TbIII single-molecule magnet (SMM) with two [TbPc2]0 units connected via a fused-phthalocyaninato ligand. The stable and robust complex [(obPc)Tb(Fused-Pc)Tb(obPc)] (1) was characterized by using synchrotron radiation measurements and other spectroscopic techniques (ESI-MS, FT-IR, UV). The magnetic couplings between the TbIII ions and the two π radicals present in 1 were explored by means of density functional theory (DFT). Direct and alternating current magnetic susceptibility measurements were conducted on magnetically diluted and nondiluted samples of 1, indicating this compound to be an SMM with improved properties compared to those of the well-known [TbPc2]-/0/+ and the axially symmetric dinuclear TbIII phthalocyaninato triple-decker complex (Tb2(obPc)3). Assuming that the probability of quantum tunneling of the magnetization (QTM) occurring in one TbPc2 unit is PQTM, the probability of QTM simultaneously occurring in 1 is PQTM2, meaning that QTM is effectively suppressed. Furthermore, nondiluted samples of 1 underwent slow magnetic relaxation times (τ ≈ 1000 s at 0.1 K), and the blocking temperature (TB) was determined to be ca. 16 K with an energy barrier for spin reversal (Ueff) of 588 cm-1 (847 K) due to D4d geometry and weak inter- and intramolecular magnetic interactions as an exchange bias (Hbias), reducing QTM. Four hyperfine steps were observed by micro-SQUID measurement. Furthermore, solution NMR measurements (one-dimensional, two-dimensional, and dynamic) were done on 1, which led to the determination of the high rotation barrier (83 ± 10 kJ/mol) of the obPc ligand. A comparison with previously reported TbIII triple-decker compounds shows that ambient temperature NMR measurements can indicate improvements in the design of coordination environments for SMMs. A large Ueff causes strong uniaxial magnetic anisotropy in 1, leading to a χax value (1.39 × 10-30 m3) that is larger than that for Tb2(obPc)3 (0.86 × 10-30 m3). Controlling the coordination environment and spin arrangement is an effective technique for suppressing QTM in TbPc2-based SMMs.

Tetranuclear Dysprosium(III) Quintuple-Decker Single-Molecule Magnet Prepared Using a π-Extended Phthalocyaninato Ligand with Two Coordination Sites.

The magnetic properties and spin relaxation processes of a tetranuclear dysprosium(III) fused phthalocyaninato (Pc4- ) quintuple-decker single-molecule magnet (SMM) (1) with non-equivalent octa-coordination geometries are reported. The structure of 1 is regarded as a dimer of Dy3+ -Pc triple-decker SMMs with different magnetic relaxation characteristics, corresponding to the octa-coordination geometry sites Dy1 with C4 symmetry (ϕ1 =23°) and Dy2 with D4d symmetry (ϕ2 =45°). In an Hdc of 1750 Oe and T range of 1.8-3.75 K, the quantum tunnelling of the magnetization was suppressed, and the direct process was enhanced. The effects of the coordination geometry on the spin relaxation phenomena are examined.

Supramolecular Approach for Enhancing Single-Molecule Magnet Properties of Terbium(III)-Phthalocyaninato Double-Decker Complexes with Crown Moieties.

A TbIII -phthalocyaninato double-decker ([1]0 ) single-molecule magnet (SMM) having four 15-crown-5 moieties in one of the ligands was synthesized, and its dimerization and magnetic properties were studied in an attempt to utilize the supramolecular aggregation for enhancing the SMM properties. Aggregation of [1]0 to form [12 K4 ]4+ in the presence of K+ ions was studied by using UV/Vis-NIR absorption and NMR spectroscopies. For the magnetic measurements, [1]0 and [12 K4 ]4+ were dispersed in poly(methyl methacrylate) (PMMA). UV/Vis-NIR absorption measurements on the PMMA dispersed samples were used to track the formation of [12 K4 ]4+ . Direct current (DC) magnetic susceptibility measurements revealed that there were ferromagnetic Tb-Tb interactions in [12 K4 ]4+ , whereas there was no indication of ferromagnetic interactions in [1]0 . Upon the formation of [12 K4 ]4+ from [1]0 and K+ ions, the temperature at which the magnetic hysteresis occurred increased from 7 to 15 K. In addition, the area of magnetic hysteresis became larger for [12 K4 ]4+ , meaning that SMM properties of [12 K4 ]4+ are superior to those of [1]0 . Alternating current (AC) magnetic measurements were used to confirm this observation. Magnetic relaxation times at 2 K increased 1000-fold upon dimerization of [1]0 to [12 K4 ]4+ , demonstrating the effectiveness of using K+ ions to induce dimer formation for the improvement of the SMM properties.

Slow Magnetic Relaxation in a Palladium-Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion.

Incorporating palladium in the first coordination sphere of acetato-bridged lanthanoid complexes, [Pd2 Ln2 (H2 O)2 (AcO)10 ]⋅2 AcOH (Ln=Gd (1), Y (2), Gd0.4 Y1.6 (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d8 Pd2+ ion to Gd3+ ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X-ray absorption near-edge structure (XANES) analysis. Field-induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre-exponential factor (τo =0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal-lanthanoid (TM-Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.

Changing Single-Molecule Magnet Properties of a Windmill-Like Distorted Terbium(III) α-Butoxy-Substituted Phthalocyaninato Double-Decker Complex by Protonation/Deprotonation.

Synthesis, structures, and magnetic properties of α-butoxy-substituted phthalocyaninato double-decker complexes Tb(α-obPc)2 (1-) (α-obPc: dianion of 1,4,8,11,15,18,22,25-octa(n-butoxy)phthalocyaninato) with protonated (1H), deprotonated (1[HDBU]), and diprotonated forms (1H2+) are discussed. X-ray analysis was used to confirm the position of the proton in 1H, and it was revealed that the protonation induced asymmetric distortion in 1H. In contrast, 1[HDBU] was distorted in a highly symmetric windmill-like fashion. 1H is arranged in a slipped column array in the crystal packing, whereas 1[HDBU] is arranged in a one-dimensional fashion, in which the magnetic easy axes of 1[HDBU] lie along the same line. From direct-current (dc) magnetic measurements, ferromagnetic Tb-Tb interactions occur in both 1H and 1[HDBU], and magnetic hysteresis was observed. However, the area of the magnetic hysteresis in 1[HDBU] is larger than that in 1H, meaning that magnetic relaxation time (τ) is longer in 1[HDBU]. In addition, the results of alternating-current magnetic measurements in a zero dc magnetic field indicate that τ of 1[HDBU] is longer as compared to 1H. In other words, protonation/deprotonation affects not only the molecular structures and crystal packing but also the single-molecule magnet properties.

Control of the Spin Dynamics of Single-Molecule Magnets by using a Quasi One-Dimensional Arrangement.

Magnetic dipole interactions are dominate in quasi one-dimensional (1D) molecular magnetic materials, in which TbNcPc units (Tb3+ =terbium(III) ion, Nc2- =naphthalocyaninato, Pc2- =phthalocyaninato) adopt a structure similar to TbPc2 single-molecule magnets (SMMs). The magnetic properties of the [TbNcPc]0/+ (neutral 1 and cationic 2) with 1D structures are significantly different from those of a magnetically diluted sample (3). In particular, the magnetic relaxation time (τ) of 2 in the low-temperature region is five orders of magnitude slower than that of 3. Furthermore, the coercivity (HC ) of 2 remained up to about 20 K. The single-ion anisotropy of Tb3+ ions in a 1D structure and the magnetic dipole interactions acting among molecules determines the direction of the magnetic properties. These results show that the spin dynamics can be improved by manipulating the arrangement of SMMs in the solid state.

Elucidation of Dual Magnetic Relaxation Processes in Dinuclear Dysprosium(III) Phthalocyaninato Triple-Decker Single-Molecule Magnets Depending on the Octacoordination Geometry.

When applying single-molecule magnets (SMMs) to spintronic devices, control of the quantum tunneling of the magnetization (QTM) as well as a spin-lattice interactions are important. Attempts have been made to use not only coordination geometry but also magnetic interactions between SMMs as an exchange bias. In this manuscript, dinuclear dysprosium(III) (DyIII ) SMMs with the same octacoordination geometry undergo dual magnetic relaxation processes at low temperature. In the dinuclear DyIII phthalocyaninato (Pc2- ) triple-decker type complex [(Pc)Dy(ooPc)Dy(Pc)] (1) (ooPc2- =2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato) with a square-antiprismatic (SAP) geometry, the ground state is divided by the Zeeman effect, and level intersection occurs when a magnetic field is applied. Due to the ground state properties of 1, since the Zeeman diagram where the levels intersect in an Hdc of 2500 Oe, two kinds of QTM and direct processes occur. However, dinuclear DyIII -Pc systems with C4 geometry, which have a twist angle (ϕ) of less than 45° do not undergo dual magnetic relaxation processes. From magnetic field and temperature dependences, the dual magnetic relaxation processes were clarified.

Molecular Orientation of a Terbium(III)-Phthalocyaninato Double-Decker Complex for Effective Suppression of Quantum Tunneling of the Magnetization.

Single-molecule magnet (SMM) properties of crystals of a terbium(III)-phthalocyaninato double-decker complex with different molecular packings (1: TbPc2, 2: TbPc2·CH2Cl2) were studied to elucidate the relationship between the molecular packing and SMM properties. From single crystal X-ray analyses, the high symmetry of the coordination environment of 2 suggested that the SMM properties were improved. Furthermore, the shorter intermolecular Tb-Tb distance and relative collinear alignment of the magnetic dipole in 2 indicated that the magnetic dipole-dipole interactions were stronger than those in 1. This was confirmed by using direct current magnetic measurements. From alternating current magnetic measurements, the activation energy for spin reversal for 1 and 2 were similar. However, the relaxation time for 2 is three orders of magnitude slower than that for 1 in the low-T region due to effective suppression of the quantum tunneling of the magnetization. These results suggest that the SMM properties of TbPc2 highly depend on the molecular packing.