Polar materials with isolated V4+ S = 1/2 Triangles: NaSr2V3O3(Ge4O13)Cl and KSr2V3O3(Ge4O13)Cl
- 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.
- 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, Journal Name: Chemistry of Materials Journal Issue: 3 Vol. 29; ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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