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

Journal Article · · Chemistry of Materials
 [1];  [2];  [1];  [2];  [1]
  1. Clemson Univ., Clemson, SC (United States)
  2. 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

References (57)

Trinuclear Fragments as Nucleation Centres: New Polyoxoalkoxyvanadates by (Induced) Self-Assembly journal August 1998
Hydrothermal Synthesis of Single Crystals book January 2007
Open-Framework Structures of Transition-Metal Compounds journal June 2008
The Versatile Chemistry and Noncentrosymmetric Crystal Structures of Salt-Inclusion Vanadate Hybrids journal May 2008
Skyrmions journal January 2013
Extending the Family of V 4+ S =${{ 1/2 }}$ Kagome Antiferromagnets journal October 2015
Hydrothermal synthesis of new compounds journal January 1991
Schiff base metal complexes as ligands1 journal December 1969
Hydrothermal synthesis of germanium vanadate layered compounds journal October 2003
A novel germanate, Cu2Fe2Ge4O13, with a four tetrahedra oligomer journal November 2003
Synthesis and structures of the layered vanadyl(IV) silico-germanates Li2VO(Si1−xGex)O4 (x = 0, 0.5, 1) journal September 1998
Synthesis, structural characterization, and magnetic properties of NaRE9(GeO4)6O2 (RE = Nd, Pr) journal March 2004
Low-dimensional magnetic materials journal April 1997
Crystal structure and magnetic behavior of Cu3(O2C16H23)6·1.2 C6H12. An unexpected structure and an example of spin frustration journal April 2001
Recent progress in first-principles studies of magnetoelectric multiferroics journal June 2005
Hydrothermal synthesis and structure of a novel hybrid germanium vanadate: (2,2 ′ -bpy) 2 (V V O 2 ) 2 (H 2 GeO 4 ) · 6H 2 O journal July 2004
Hydrothermal synthesis and characterization of a new layered compound Li2VGeO5 journal May 2004
Multiferroics—toward strong coupling between magnetization and polarization in a solid journal March 2007
Cu2Sc2Ge4O13, a novel germanate isotypic with the quasi-1D compound Cu2Fe2Ge4O13 between 100 and 298K journal August 2004
Hydrothermal synthesis of single crystals of transition metal vanadates in the glaserite phase journal April 2016
Hydrothermal synthesis, characterization and magnetic properties of NaVGe2O6 and LiVGe2O6 journal August 2004
Hydrothermal synthesis, structure, and property characterization of rare earth silicate compounds: NaBa3Ln3Si6O20 (Ln = Y, Nd, Sm, Eu, Gd) journal October 2015
Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior journal July 2015
Hydrothermal Single-Crystal Growth of Lu 2 O 3 and Lanthanide-Doped Lu 2 O 3 journal October 2011
Host−Guest Symmetry and Charge Matching in Two Germanates with Intersecting Three-Dimensional Channels journal June 2000
Hydrothermal Synthesis of Vanadium Oxides journal October 1998
Crystal Chemical Aspects of Vanadium:  Polyhedral Geometries, Characteristic Bond Valences, and Polymerization of (VO n ) Polyhedra journal May 2000
Polyoxometalates:  Very Large ClustersNanoscale Magnets journal February 1998
Vanadogermanate Cluster Anions journal May 2003
Syntheses and magnetic properties of N-[2-(2-hydroxyethylthio)phenyl]arenesulfonamidatocopper(II) chelates journal November 1968
EPR and magnetic susceptibility studies of the trinuclear complex cyanuratotris[bis(.eta.5-methylcyclopentadienyl)titanium(III)], the binuclear complex uracilatobis[bis(.eta.5-methylcyclopentadienyl)titanium(III)], and related compounds journal July 1978
Hydrothermal Growth of Lanthanide Borosilicates: A Useful Approach to New Acentric Crystals Including a Derivative of Cappelenite journal November 2014
Trinuclear N,N-Bridged Copper(II) Complexes Involving a Cu 3 OH Core:  [Cu 33 -OH)L 3 A(H 2 O) 2 ]A·(H 2 O) x {L = 3-Acetylamino-1,2,4-triazolate; A = CF 3 SO 3 , NO 3 , ClO 4 ; x = 0, 2} Synthesis, X-ray Structures, Spectroscopy, and Magnetic Properties journal May 2000
A New Class of Hybrid Materials via Salt Inclusion:  Novel Copper(II) Arsenates Na 5 ACu 4 (AsO 4 ) 4 Cl 2 (A = Rb, Cs) Composed of Alternating Covalent and Ionic Lattices journal October 2002
Salt-Templated Open Frameworks (CU-2):  Novel Phosphates and Arsenates Containing M 3 (X 2 O 7 ) 2 2- (M = Mn, Cu; X = P, As) Micropores 5.3 Å and 12.7 Å in Diameter journal November 1999
Multiferroic and magnetoelectric materials journal August 2006
Spontaneous skyrmion ground states in magnetic metals journal August 2006
Multiferroics: a magnetic twist for ferroelectricity journal January 2007
Possible valence-bond condensation in the frustrated cluster magnet LiZn2Mo3O8 journal May 2012
Strong spin frustration from isolated triangular Cu( ii ) trimers in SrCu(OH) 3 Cl with a novel cuprate layer journal January 2014
Hydrothermal synthesis as a route to mineralogically-inspired structures journal January 2016
Geometrically frustrated magnetic materials journal January 2001
Classical spin and quantum-mechanical descriptions of geometric spin frustration journal July 2004
Effective Field Theories of Magnetism journal August 1966
Bulk single crystal growth from hydrothermal solutions journal July 2012
Heisenberg spin triangles in { V 6 } -type magnetic molecules: Experiment and theory journal August 2002
Inelastic neutron scattering study of a quantum spin trimer journal June 2007
Structural and magnetic characterization of the one-dimensional S = 5 / 2 antiferromagnetic chain system SrMn ( V O 4 ) ( OH ) journal June 2016
Molecular Quantum Magnetism in LiZn 2 Mo 3 O 8 journal January 2014
Ba 2 Gd 2 (Si 4 O 13 ): a silicate with finite Si 4 O 13 chains journal February 2010
A short history of SHELX journal December 2007
Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database journal August 1985
Bond-valence parameters for solids journal April 1991
Structural chemistry of vanadium oxides with open frameworks journal October 1999
Use of intensity quotients and differences in absolute structure refinement journal May 2013
Surprises on the Way from One- to Two-Dimensional Quantum Magnets: The Ladder Materials journal February 1996
Strongly Geometrically Frustrated Magnets journal August 1994

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