Yin-Shan Meng

Cobalt(II) coordination polymer exhibiting single-ion-magnet-type field-induced slow relaxation behavior.

A one-dimensional cobalt(II) coordination polymer, [Co(btm)2(SCN)2·H2O]n [btm = bis(1H-1,2,4-triazol-1-yl)methane], was synthesized and magnetically characterized. The isolated slightly distorted octahedral Co(II) ion displays field-induced slow relaxation with a big positive axial and a negative rhombic magnetic anisotropy (D = 93.9 cm(-1) and E = -10.5 cm(-1)), and the anisotropy energy barrier is 45.4 K.

Half-Sandwich Complexes of DyIII: A Janus-Motif with Facile Tunability of Magnetism

Three half-sandwich organometallics [(Cp(R))Dy(DBM)2(THF)]·solvent [Cp(R) = Cp* (1Dy, Cp* = C5Me5), Cp(4PrPh) (2Dy, Cp(4PrPh) = C5Pr4Ph), Cp (3Dy, Cp = C5Me4TMS, solvent = THF), DBM(-) = dibenzoylmethanoate anion, THF = tetrahydrofuran, TMS = trimethylsilyl] with a Janus structural motif, where the ligands of DBM(-) and [Cp(R)](-) are widely used in Dy(III)/β-diketonate and Ln(III)/cyclopentadienyl systems, were synthesized, structurally and magnetically characterized, and theoretically investigated. Single-crystal structural analysis reveals that the three complexes crystallize in the same space group P21/c. All the molecules display slow magnetic relaxation in the absence of an applied magnetic field, and the magnetic hysteresis loops of 2Dy and 3Dy can be observed under a magnetic field sweep rate of 10 Oe/s, indicating all three complexes are single-ion magnets (SIMs). The modifications of the Cp-ring lead to the distinct increment of the energy barrier from 46 K (1Dy) to 76 K (2Dy) to 320 K (3Dy). Ab initio calculations show that the ground Kramers doublet is strongly axial with gz approaching the value of 20 expected for the pure MJ = ±15/2 state, and the magnetic anisotropy axes for three complexes share a similar orientation which is perpendicular to the molecular pseudosymmetric axis. Electrostatic analyses confirm the magnetic anisotropy orientations and reveal that proper charge distribution of the coordination sphere (including the first and second) around Dy(III) ion enhances the magnetic anisotropy. Further investigation of the relaxation mechanisms suggests the energy barrier should be carefully used to evaluate single-ion magnets if Raman process is dominant in the low temperature range.

Tuning Slow Magnetic Relaxation in a Two-Dimensional Dysprosium Layer Compound through Guest Molecules.

A novel two-dimensional dysprosium(III) complex, [Dy(L)(CH3COO)]·0.5DMF·H2O·2CH3OH (1), has been successfully synthesized from a new pyridine-N-oxide (PNO)-containing ligand, namely, N-(2-hydroxy-3-methoxybenzylidene)pyridine-N-oxidecarbohydrazide (H2L). Single-crystal X-ray diffraction studies reveal that complex 1 is composed of a dinuclear dysprosium subunit, which is further extended by the PNO part of the ligand to form a two-dimensional layer. Magnetic studies indicate that complex 1 shows well-defined temperature- and frequency-dependent signals under a zero direct-current (dc) field, typical of slow magnetic relaxation with an effective energy barrier Ueff of 33.6 K under a zero dc field. Interestingly, powder X-ray diffraction and thermogravimetric analysis reveal that compound 1 undergoes a reversible phase transition that is induced by the desorption and absorption of methanol and water molecules. Moreover, the desolvated sample [Dy(L)(CH3COO)]·0.5DMF (1a) also exhibits slow magnetic relaxation but with a higher anisotropic barrier of 42.0 K, indicating the tuning effect of solvent molecules on slow magnetic relaxation.

Slow Magnetic Relaxation in Weak Easy-Plane Anisotropy: the Case of a Combined Magnetic and HFEPR Study

Two pseudotetrahedral cobalt(II) complexes exhibiting slow magnetic relaxation under an applied direct-current field are investigated. The weak easy-plane anisotropy is accurately determined by high-field/high-frequency electron paramagnetic resonance spectroscopy as D = 2.57 cm-1 and E = 0.82 cm-1 for 1 and D = 5.56 cm-1 and E = 1.05 cm-1 for 2. In addition, hysteresis loops are observed for the two compounds at very low temperatures.

Synergic on/off Photoswitching Spin State and Magnetic Coupling between Spin Crossover Centers

The existence of a correlation between spin crossover and dielectric properties is a hot topic in the field of multiresponse materials, which has potential applications in the memory devices, switches, and sensors. One formidable challenge is the simultaneous and rapid on/off switching of spin states of the spin carriers and magnetic coupling between them, which is crucial for both reversible photomagnetic behavior and variations in dielectric properties. Here, we report a dinuclear Fe(II) spin crossover complex, wherein each Fe(II) center exhibits an interconversion between FeIIHS (HS = high-spin) and FeIILS (LS = low-spin) achieved upon heating and cooling. Moreover, the spin state of respective Fe(II) ions and the antiferromagnetic interaction between them can be switched bidirectionally under alternating irradiation with 532 and 808 nm light, resulting in interconversion between paramagnetic and diamagnetic properties. Interestingly, the spin crossover can also induce variations in dielectric tensors. This result provides a strategy to simultaneously and bidirectionally switch spin state, magnetic coupling, and dielectric properties using external stimuli.

A Six-Coordinate Dysprosium Single-Ion Magnet with Trigonal-Prismatic Geometry

A mononuclar six-coordinate dysprosium complex was synthesized and structurally and magnetically characterized. X-ray structural analyses show trigonal-prismatic coordination geometry of the DyIII center. Slow relaxation of magnetization in the absence of a direct-current field and magnetic hysteresis up to 3.0 K could be observed, indicating its single-ion-magnet behavior. Arrhenius fitting and ab initio calculations suggest that the magnetic relaxation process may not occur through the Orbach process at high temperatures under the experimental conditions.

A Material Showing Colossal Positive and Negative Volumetric Thermal Expansion with Hysteretic Magnetic Transition

It is an ongoing challenge to design and synthesize magnetic materials that undergo colossal thermal expansion and that possess potential applications as microscale or nanoscale actuators with magnetic functionality. A paramagnetic metallocyanate building block was used to construct a cyanide-bridged Fe-Co complex featuring both positive and negative colossal volumetric thermal-expansion behavior. A detailed study revealed that metal-to-metal charge transfer between 180 and 240u2005K induced a volumetric thermal expansion coefficient of 1498u2005MK-1 accompanied with hysteretic spin transition. Rotation of the magnetic building blocks induced change of π⋅⋅⋅π interactions, resulting in a negative volume expansion coefficient of -489u2005MK-1 , and another hysteretic magnetic transition between 300 and 350u2005K. This work presents a strategy for incorporating both colossal positive and negative volumetric thermal expansion with shape and magnetic memory effects in a material.

A Series of Linear {FeIII2FeII} Complexes with Paramagnetic Building‐Block‐Modified Spin Crossover Behaviors

Tuning of the spin crossover (SCO) behavior through paramagnetic building blocks with different steric hindrance effects is of great interest in terms of the synergy between SCO and magnetic interactions. Herein, the steric effect of specified FeIII building blocks is modified, from the large Tp* (hydridotris(3,5-dimethylpyrazol-1-yl)borate) analogue to a small Tp (hydrotris(pyrazolyl)borate) derivative; the FeII SCO unit and FeIII paramagnetic ions are incorporated into three well isolated trinuclear complexes featuring thermally induced and light-induced SCO properties. Reanalysis of the structures reveals that π-π stacking interactions play a key role in the thermal hysteresis and anomalous octahedral distortion parameter Σ around the FeII ion. The Tp* ligand showing the largest steric hindrance induces elongated FeII -N bond lengths and bending of the C≡N-FeII angle in 1, as well as having a relatively large electron donor effect, which leads to the lowest thermal transition temperature among the three compounds.

Manipulating Metal‐to‐Metal Charge Transfer for Materials with Switchable Functionality

Metal-to-metal charge transfer (MMCT) describes electron transfer between metal ions, to generate valence isomers with markedly different electronic configurations. In particular, MMCT changes the spin states of single-metal sites and the coupling interactions between them, while also changing the symmetry in charge distribution. The result is a drastic change in both magnetic and electric properties of the affected material. Moreover, MMCT causes significant variation in bond length and absorption spectra, and induces unusual thermal expansion and photochromic behavior. Thus, materials demonstrating MMCT in response to external stimuli are excellent candidates for switchable multifunctional devices with synergistic responses. In this Minireview, recent progress in utilizing MMCT units as actuators to tune magnetic, electric, thermal expansion, and photochromic properties in cyanide-bridged systems is highlighted, and emphasis is given to the remaining challenges and future perspectives in the field.

Simultaneous Modulation of Magnetic and Dielectric Transition via Spin‐Crossover‐Tuned Spin Arrangement and Charge Distribution

Magnetic and dielectric properties have been tuned simultaneously by external stimuli with rapid and sensitive response, which is crucial to monitor the magnetic state via capacitive measurement. Herein, positive charged FeII ions were linked via negative charged [(Tp)FeIII (CN)3 ]- (Tp=hydrotris(pyrazolyl)borate) units to form a neutral chain. The spin-crossover (SCO) on FeII sites could be sensitively triggered via thermal treatment, light irradiation, and pressure. SCO switched the spin state of the FeII ions and antiferromagnetic interactions between FeIII and FeII ions, resulting in significant change in magnetization. Moreover, SCO induced rotation of negative charged [(Tp)FeIII (CN)3 ]- units, generating dielectric anomaly due to geometric change of charges distribution. This work provides a rational way to manipulate simultaneous variations in magnetic and dielectric properties utilizing SCO as an actuator to tune spin arrangement, magnetic coupling, and charge distribution.