skip to main content

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Friday, March 22 until 6:00 AM ET on Saturday, March 23 due to maintenance. We apologize for the inconvenience.


Title: Crystal growth and physical properties of an antiferromagnetic molecule: trans -dibromidotetrakis(acetonitrile)chromium(III) tribromide, [CrBr 2 (NCCH 3 ) 4 ](Br 3 )
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.  more » « less
Award ID(s):
2053287
NSF-PAR ID:
10314105
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials
Volume:
77
Issue:
4
ISSN:
2052-5206
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I , Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P 3̄1 c , and compound II , K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P 6 3 / m . Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c -axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab -plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6 -honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 ( II ) exhibits a canted antiferromagnetic ordering below T N = 8 K. The Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of −42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices. 
    more » « less
  2. A novel antiferromagnetic semiconductor, Eu 3 Sn 2 P 4 , has been discovered. Single crystals of Eu 3 Sn 2 P 4 were prepared using the Sn self-flux method. The crystal structure determined by single crystal X-ray diffraction shows that Eu 3 Sn 2 P 4 crystallizes in the orthorhombic structure with the space group Cmca (Pearson Symbol, oP 216). Six Sn–Sn dimers connected by P atoms form a Sn 12 P 24 crown-shaped cluster with a Eu atom located in the center. Magnetization measurements indicate that the system orders antiferromagnetically below a T N ∼14 K at a low field and undergoes a metamagnetic transition at a high field when T < T N . The effective magnetic moment is 7.41(3) μ B per Eu, corresponding to Eu 2+ . The electric resistivity reveals a non-monotonic temperature dependence with non-metallic behavior below ∼60 K, consistent with the band structure calculations. By fitting the data using the thermally activated resistivity formula, we estimate the energy gap to be ∼0.14 eV. Below T N , the resistivity tends to saturate, suggesting the reduction of charge-spin scattering. 
    more » « less
  3. Abstract

    Magnetic van der Waals (vdW) materials are the centerpiece of atomically thin devices with spintronic and optoelectronic functions. Exploring new chemistry paths to tune their magnetic and optical properties enables significant progress in fabricating heterostructures and ultracompact devices by mechanical exfoliation. The key parameter to sustain ferromagnetism in 2D is magnetic anisotropy—a tendency of spins to align in a certain crystallographic direction known as easy‐axis. In layered materials, two limits of easy‐axis are in‐plane (XY) and out‐of‐plane (Ising). Light polarization and the helicity of topological states can couple to magnetic anisotropy with promising photoluminescence or spin‐orbitronic functions. Here, a unique experiment is designed to control the easy‐axis, the magnetic transition temperature, and the optical gap simultaneously in a series of CrCl3−xBrxcrystals between CrCl3withXYand CrBr3with Ising anisotropy. The easy‐axis is controlled between the two limits by varying spin–orbit coupling with the Br content in CrCl3−xBrx. The optical gap, magnetic transition temperature, and interlayer spacing are all tuned linearly withx. This is the first report of controlling exchange anisotropy in a layered crystal and the first unveiling of mixed halide chemistry as a powerful technique to produce functional materials for spintronic devices.

     
    more » « less
  4. Abstract

    While induced spin polarization of a palladium (Pd) overlayer on antiferromagnetic and magneto-electric Cr2O3(0001) is possible because of the boundary polarization at the Cr2O3(0001), in the single domain state, the Pd thin film appears to be ferromagnetic on its own, likely as a result of strain. In the conduction band, we find the experimental evidence of ferromagnetic spin polarized in Pd thin films on a Cr2O3(0001) single crystal, especially in the thin limit, Pd thickness of around 1–4 nm. Indeed there is significant spin polarization in 10 Å thick Pd films on Cr2O3(0001) at 310 K, i.e. above the Néel temperature of bulk Cr2O3. While Cr2O3(0001) has surface moments that tend to align along the surface normal, for Pd on Cr2O3, the spin polarization contains an in-plane component. Strain in the Pd adlayer on Cr2O3(0001) appears correlated to the spin polarization measured in spin polarized inverse photoemission spectroscopy. Further evidence for magnetization of Pd on Cr2O3is provided by measurement of the exchange bias fields in Cr2O3/Pd(buffer)/[Co/Pd]nexchange bias systems. The magnitude of the exchange bias field is, over a wide temperature range, virtually unaffected by the Pd thickness variation between 1 and 2 nm.

     
    more » « less
  5. The results of the structural determination, magnetic characterization, and theoretical calculations of a new ruthenium-oxo complex, Li 4 [Ru 2 OCl 10 ]·10H 2 O, are presented. Single crystals were grown using solvent methods and the crystal structure was characterized by single crystal X-ray diffraction. Li 4 [Ru 2 OCl 10 ]·10H 2 O crystallizes into a low-symmetry triclinic structure ( P 1 ) due to the much smaller Li + cation compared to K + cation in the tetragonal complex K 4 [Ru 2 OCl 10 ]·H 2 O. The X-ray photoelectron spectra confirm only the single valent Ru 4+ in Li 4 [Ru 2 OCl 10 ]·10H 2 O even though two distinct Ru sites exist in the crystal structure. Magnetic measurements reveal the diamagnetic property of Li 4 [Ru 2 OCl 10 ]·10H 2 O with unpaired electrons existing on Ru 4+ . Furthermore, the molecular orbital analysis matches well with the observed UV and magnetic measurements. 
    more » « less