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1.
Inorg Chem ; 60(2): 872-882, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33355450

RESUMO

We report the synthesis, structure, and redox behavior of the cation-ordered tetragonal Sc2VO5+δ defect fluorite superstructure previously thought to be the oxygen precise A3+2B4+O5 phase. Four synthesis routes in oxidative, reductive, and inert atmospheres are demonstrated. Ex situ and in situ powder X-ray and neutron diffraction analyses reveal vanadium disproportionation reactions. The structure-reaction map illustrates the oxygen-dependent competition between the tetragonal cation and anion ordered Sc2VO5+δ and the disordered cubic Sc2VO5+δ' (δ < δ' ≤ 0.5) phases as a function of temperature. Oxidation states and oxide stoichiometries were determined with DC magnetometry and XANES experiments. The tetragonal cation ordered Sc2VO5+δ phase with δ = -0.15(2) for as-synthesized samples reveals vanadium charge ordering. V3+ and V4+ cations occupy octahedral sites, whereas V5+ predominantly occupies a tetrahedral site. The paramagnetic 8g{V3+/4+}4 clusters are isolated by diamagnetic 2cV5+ cations. At temperatures below 500 °C the 8g{V3+/4+}4 clusters can be topotactically fine-tuned with varying V3+/V4+ ratios. Above 600 °C the tetragonal structure oxidizes to the cubic Sc2VO5+δ' fluorite phase-its disordered competitor. The investigation of the cation- and anion-ordered Sc-V-O phases, their formation, and thermal stability is important for the design of low-temperature solid state oxide ion conductors and vacancy structures.

2.
Inorg Chem ; 55(24): 12897-12903, 2016 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-27989196

RESUMO

The crystal structure of KRuO4 is refined at both 280 and 3.5 K from neutron powder data, and magnetic properties are reported for the first time. The scheelite structure, I41/a, is confirmed at both temperatures. Atomic positions of greater accuracy than the original 1954 X-ray study are reported. The rare Ru7+ ion resides in a site of distorted tetrahedral symmetry with nominal electronic configuration 4d1(e1). Curie-Weiss parameters are near free ion values for the effective moment and θ = -77 K, indicating dominant antiferromagnetic (AF) correlations. A broad susceptibility maximum occurs near 34 K, but long-range AF order sets in only below 22.4 K as determined by magnetization and heat capacity data. The entropy loss below 50 K is only 44% of the expected R ln 2, indicating the presence of short-range spin correlations over a wide temperature range. The Ru sublattice consists of centered, corner-sharing tetrahedra which can lead to geometric frustration if both the nearest-neighbor, J1, and the next-nearest-neighbor, J2, exchange constants are AF and of similar magnitude. A spin dimer analysis finds J1/J2 ≈ 25, indicating weak frustration, and a (dz2)1 ground state. A single, weak magnetic reflection was indexed as (110). The absence of the (002) magnetic reflection places the Ru moments parallel to the c axis. The Ru7+ moment is estimated to be 0.57(7) µB, reduced from an expected value near 1 µB. A recent computational study of isostructural, isoelectronic KOsO4 predicts a surprisingly large orbital moment due to spin-orbit coupling (SOC). However, the free ion SOC constant for Ru7+ is only ∼30% that of Os7+, so it is unclear that this effect can be implicated in the low ordered moment for KRuO4. The origin of the short-range spin correlations is also not understood.

3.
Chem Commun (Camb) ; 57(50): 6213-6216, 2021 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-34059865

RESUMO

We describe the structural and magnetic properties of a tetranuclear [2 × 2] Co4 grid complex containing a ditopic arylazo ligand. At low temperatures and in solution the complex is comprised of Co3+ and singly reduced trianion-radical ligands. In the solid state we demonstrate the presence of valence tautomerization via variable temperature magnetic susceptibility experiments and powder-pattern EPR spectroscopy. Valence tautomerism in polynuclear complexes is very rare and to our knowledge is unprecedented in [2 × 2] grid complexes.

4.
J Phys Condens Matter ; 32(13): 134001, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-31775126

RESUMO

Typically, quantum spin liquid candidates can be found in materials with a combination of geometrical frustration along with low spin. Due to its spin of S = 1/2 the copper (II) ion is often present in the discussion on spin liquid candidates. The solid state compound Ca3Cu2GeV2O12 is a material that crystallizes in the garnet structure (s.g. #230, Ia-3d), where 3D frustration is known to occur. Heat capacity has shown a lack of magnetic ordering down to 0.35 K, confirmed with low temperature neutron diffraction to 0.07 K. This system displays a Weiss temperature of -0.93(1) K indicating net antiferromagnetic interactions and significant J 1-J 2 competition causing frustration. Using both neutron and x-ray diffraction along with heat capacity and magnetometry, the work presented here shows Ca3Cu2GeV2O12 has potential as a new spin liquid candidate.

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