The synthesis, crystal structure determination, magnetic properties and bonding interaction analysis of a novel 3 d transition-metal complex, [CrBr 2 (NCCH 3 ) 4 ](Br 3 ), are reported. Single-crystal X-ray diffraction results show that [CrBr 2 (NCCH 3 ) 4 ](Br 3 ) crystallizes in space group C 2/ m (No. 12) with a symmetric tribromide anion and the powder X-ray diffraction results show the high purity of the material specimen. X-ray photoelectron studies with a combination of magnetic measurements demonstrate that Cr adopts the 3+ oxidation state. Based on the Curie–Weiss analysis of magnetic susceptibility data, the Néel temperature is found to be around 2.2 K and the effective moment (μ eff ) of Cr 3+ in [CrBr 2 (NCCH 3 ) 4 ](Br 3 ) is ∼3.8 µ B , which agrees with the theoretical value for Cr 3+ . The direct current magnetic susceptibility of the molecule shows a broad maximum at ∼2.3 K, which is consistent with the theoretical Néel temperature. The maximum temperature, however, shows no clear frequency dependence. Combined with the observed upturn in heat capacity below 2.3 K and the corresponding field dependence, it is speculated that the low-temperature magnetic feature of a broad transition in [CrBr 2 (NCCH 3 ) 4 ](Br 3 ) could originate from a crossover from high spin to low spin for the split d orbital level low-lying states rather than a short-range ordering solely; this is also supported by the molecular orbital diagram obtained from theoretical calculations.
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Magnetic Field Perturbations to a Soft X-ray-Activated Fe (II) Molecular Spin State Transition
The X-ray-induced spin crossover transition of an Fe (II) molecular thin film in the presence and absence of a magnetic field has been investigated. The thermal activation energy barrier in the soft X-ray activation of the spin crossover transition for [Fe{H2B(pz)2}2(bipy)] molecular thin films is reduced in the presence of an applied magnetic field, as measured through X-ray absorption spectroscopy at various temperatures. The influence of a 1.8 T magnetic field is sufficient to cause deviations from the expected exponential spin state transition behavior which is measured in the field free case. We find that orbital moment diminishes with increasing temperature, relative to the spin moment in the vicinity of room temperature.
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- NSF-PAR ID:
- 10313700
- Date Published:
- Journal Name:
- Magnetochemistry
- Volume:
- 7
- Issue:
- 10
- ISSN:
- 2312-7481
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract In this work, we provide clear evidence of magnetic anisotropy in the local orbital moment of a molecular thin film based on the SCO complex [Fe(H2B(pz)2)2(bipy)] (pz = pyrazol−1−yl, bipy = 2,2′−bipyridine). Field dependent x-ray magnetic circular dichroism measurements indicate that the magnetic easy axis for the orbital moment is along the surface normal direction. Along with the presence of a critical field, our observation points to the existence of an anisotropic energy barrier in the high-spin state. The estimated nonzero coupling constant of ∼2.47 × 10−5eV molecule−1indicates that the observed magnetocrystalline anisotropy is mostly due to spin–orbit coupling. The spin- and orbital-component anisotropies are determined to be 30.9 and 5.04 meV molecule−1, respectively. Furthermore, the estimated
g factor in the range of 2.2–2.45 is consistent with the expected values. This work has paved the way for an understanding of the spin-state-switching mechanism in the presence of magnetic perturbations. -
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Abstract The Fe(II) spin crossover complex [Fe{H2B(pz)2}2(bipy)] (pz = pyrazol‐1‐yl, bipy = 2,2′‐bipyridine) can be locked in a largely low‐spin‐state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO2and Al2O3, or in powder samples by mixing with the strongly dipolar zwitterionic
p ‐benzoquinonemonoimine C6H2(—⋯ NH2)2(—⋯ O)2. Remarkably, it is found in both cases that incident X‐ray fluences then restore the [Fe{H2B(pz)2}2(bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light‐ or X‐ray‐induced excited‐spin‐state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment. -
null (Ed.)For the spin crossover coordination polymer [Fe(L1)(bipy)] n (where L1 is a N 2 O 2 2− coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4′-bipyridine), there is compelling additional evidence of a spin state transition. Both Fe 2p X-ray absorption and X-ray core level photoemission spectroscopies confirm that a spin crossover takes place, as observed by magnetometry. Yet the details of the temperature dependent changes of the spin state inferred from both X-ray absorption and X-ray core level photoemission, differ from magnetometry, particularly with regard to the apparent critical transition temperatures and the cooperative nature of the curve progression in general. Comparing the experimental spin crossover data to Ising model simulations, a transition activation energy in the region of 160 to 175 meV is indicated, along with a nonzero exchange J . Overall, the implication is that there may be perturbations to the bistability of spin states, that are measurement dependent or that the surface differs from the bulk with regard to the cooperative effects observed upon spin transition.more » « less
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null (Ed.)We present structural, magnetic, and optical properties of hexagonal HoFeO3/Al2O3 thin films deposited by Magnetron Sputtering. The x-ray diffraction patterns of HoFeO3 thin films show the c-planes of a hexagonal structure. The magnetization data display an antiferromagnetic transition temperature, TN∼120 ± 5 K and the magnetization-field hysteresis loops were measured below 100 K, confirming a weak ferromagnetism arising from a spin canting of the Fe3+ moments. The magnetization data also show an anomaly around ∼40 K due to a spin-reorientation transition caused by the Ho3+- Fe3+ interactions. We observed comparable magnetization along the ab plane and c axis although the spin canting of Fe3+ sites has a preferential component along the c axis, suggesting that the Ho3+- Fe3+ interactions dominate in the low temperature magnetic structures of hexagonal-HoFeO3. The observed electronic excitations at ∼2.29, 2.87, 3.82, 4.79, and 6.53 eV have been assigned to the Fe3+ d to d on-site as well as O 2p to Fe 3d, Ho 6s, and 5d charge-transfer excitations, respectively. The room temperature energy band gap of the hexagonal-HoFeO3 thin film was measured to be ∼1.99 ± 0.04 eV.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/magnetochemistry7100135
