- NSF-PAR ID:
- Date Published:
- Journal Name:
- Dalton Transactions
- Page Range / eLocation ID:
- 15359 to 15369
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Structural distortions such as cation off-centering are frustrated in the pyrochlore structure due to the triangular arrangement of cations on the pyrochlore lattice. This geometric constraint inhibits a transition from a paraelectric to ferroelectric phase in majority of pyrochlore oxide materials. Few pyrochlore materials can overcome this frustration and exhibit polar crystal structures, and unraveling the origin of such leads to the understanding of polarity in complex materials. Herein we hypothesize that frustration on the pyrochlore lattice can be relieved through A -site doping with rare earth cations that do not possess stereochemically active lone pairs. To assess if frustration is relieved, we have analyzed cation off-centering in various Bi 2−x RE xTi 2 O 7 ( RE = Y 3+ , Ho 3+ ) pyrochlores through neutron and X-ray total scattering. Motivated by known distortions from the pyrochlore literature, we present our findings that most samples show local distortions similar to the β-cristobalite structure. We additionally comment on the complexity of factors that play a role in the structural behavior, including cation size, bond valence, electronic structure, and magnetoelectronic interactions. We posit that the addition of magnetic cations on the pyrochlore lattice may play a role in an extension of the real-space correlation length of electric dipoles in the Bi-Ho series, and offer considerations for driving long-range polarity on the pyrochlore lattice.more » « less
A novel transition metal chalcohalide [Cr7S8(en)8Cl2]Cl3 ⋅ 2H2O, with [Cr7S8]5+dicubane cationic clusters, has been synthesized by a low temperature solvothermal method, using dimethyl sulfoxide (DMSO) and ethylenediamine (
en) solvents. Ethylenediamine ligand exhibits bi‐ and monodentate coordination modes; in the latter case ethylenediamine coordinates to Cr atoms of adjacent clusters, giving rise to a 2D polymeric structure. Although magnetic susceptibility shows no magnetic ordering down to 1.8 K, a highly negative Weiss constant, θ=−224(2) K, obtained from Curie‐Weiss fit of inverse susceptibility, suggests strong antiferromagnetic (AFM) interactions between S=3/2 Cr(III) centers. Due to the complexity of the system with (2 S+1)7=16384 microstates from seven Cr3+centers, a simplified model with only two exchange constants was used for simulations. Density‐functional theory (DFT) calculations yielded the two exchange constants to be J1=−21.4 cm−1and J2=−30.2 cm−1, confirming competing AFM coupling between the shared Cr3+center and the peripheral Cr3+ions of the dicubane cluster. The best simulation of the experimental data was obtained with J1=−20.0 cm−1and J2=−21.0 cm−1, in agreement with the slightly stronger AFM exchange within the triangles of the peripheral Cr3+ions as compared to the AFM exchange between the central and peripheral Cr3+ions. This compound is proposed as a synthon towards magnetically frustrated systems assembled by linking dicubane transition metal‐chalcogenide clusters into polymeric networks.
The layered perovskite Ca3Mn2O7(CMO) is a hybrid improper ferroelectric candidate proposed for room temperature multiferroicity, which also displays negative thermal expansion behavior due to a competition between coexisting polar and nonpolar phases. However, little is known about the atomic-scale structure of the polar/nonpolar phase coexistence or the underlying physics of its formation and transition. In this work, we report the direct observation of double bilayer polar nanoregions (db-PNRs) in Ca2.9Sr0.1Mn2O7using aberration-corrected scanning transmission electron microscopy (S/TEM). In-situ TEM heating experiments show that the db-PNRs can exist up to 650 °C. Electron energy loss spectroscopy (EELS) studies coupled with first-principles calculations demonstrate that the stabilization mechanism of the db-PNRs is directly related to an Mn oxidation state change (from 4+ to 2+), which is linked to the presence of Mn antisite defects. These findings open the door to manipulating phase coexistence and achieving exotic properties in hybrid improper ferroelectric.
KBiNb 2 O 7 was prepared from RbBiNb 2 O 7 by a sequence of cation exchange reactions which first convert RbBiNb 2 O 7 to LiBiNb 2 O 7 , before KBiNb 2 O 7 is formed by a further K-for-Li cation exchange. A combination of neutron, synchrotron X-ray and electron diffraction data reveal that KBiNb 2 O 7 adopts a polar, layered, perovskite structure (space group A 11 m ) in which the BiNb 2 O 7 layers are stacked in a (0, ½, z ) arrangement, with the K + cations located in half of the available 10-coordinate interlayer cation sites. The inversion symmetry of the phase is broken by a large displacement of the Bi 3+ cations parallel to the y -axis. HAADF-STEM images reveal that KBiNb 2 O 7 exhibits frequent stacking faults which convert the (0, ½, z ) layer stacking to (½, 0, z ) stacking and vice versa , essentially switching the x - and y -axes of the material. By fitting the complex diffraction peak shape of the SXRD data collected from KBiNb 2 O 7 it is estimated that each layer has approximately a 9% chance of being defective – a high level which is attributed to the lack of cooperative NbO 6 tilting in the material, which limits the lattice strain associated with each fault.more » « less
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