Polar materials with isolated V4+ S = 1/2 Triangles: NaSr2V3O3(Ge4O13)Cl and KSr2V3O3(Ge4O13)Cl

Sanjeewa, Liurukara D.; McGuire, Michael A.; McMillen, Colin D.; Garlea, Vasile O.; Kolis, Joseph W.

doi:10.1021/acs.chemmater.6b05320

Title: Polar materials with isolated V⁴⁺ S = 1/2 Triangles: NaSr₂V₃O₃(Ge₄O₁₃)Cl and KSr₂V₃O₃(Ge₄O₁₃)Cl

Journal Article · Tue Jan 03 00:00:00 EST 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b05320· OSTI ID:1350950

Sanjeewa, Liurukara D. ^[1]; McGuire, Michael A. ^[2]; McMillen, Colin D. ^[1]; Garlea, Vasile O. ^[2]; Kolis, Joseph W. ^[1]

Clemson Univ., Clemson, SC (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Here, crystals of ASr₂V₃O₃(Ge₄O₁₃)Cl, A = Na, K, were synthesized from high-temperature hydrothermal brines, and their structure and magnetic properties were investigated. These materials present a unique combination of a salt inclusion lattice, a polar crystal structure, and isolated V⁴⁺ (S = 1/2) trimer magnetic clusters. The structures consist of a trimeric V₃O₁₃ unit based on V⁴⁺ (S = 1/2), having rigorous 3-fold symmetry with a short V–V separation of 3.325(3) Å. The trinuclear V⁴⁺ units are formed by three edge shared VO₆ octahedra sharing a central μ3-oxygen atom, which also imparts a polar sense on the structure. The V₃O₁₃ units are isolated from one another by tetranuclear Ge₄O₁₃ units, which are similarly arranged in a polar fashion, providing a unique opportunity to study the magnetic behavior of this triangular d¹ system as a discrete unit. Magnetization measurements indicate spin-1/2 per V atom at high temperature, and spin-1/2 per V₃ trimer at low temperature, where two V moments in each triangle are antiferromagnetically aligned and the third remains paramagnetic. The crossover between these two behaviors occurs between 20 and 100 K and is well-described by a model incorporating strong antiferromagnetic intra-trimer interactions and weak but nonzero inter-trimer interactions. More broadly, the study highlights the ability to obtain new materials with interesting structure–property relationships via chemistry involving unconventional solvents and reaction conditions.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1350950

Journal Information:: Chemistry of Materials, Vol. 29, Issue 3; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Title: Polar materials with isolated V4+ S = 1/2 Triangles: NaSr2V3O3(Ge4O13)Cl and KSr2V3O3(Ge4O13)Cl

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Title: Polar materials with isolated V⁴⁺ S = 1/2 Triangles: NaSr₂V₃O₃(Ge₄O₁₃)Cl and KSr₂V₃O₃(Ge₄O₁₃)Cl