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Title: Divergent Structural Chemistry of Uranyl Borates Obtained from Solid State and Hydrothermal Conditions

Journal Article · · Crystal Growth and Design
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, Jülich (Germany)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Jiangsu (China)
  4. Institute of Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, Jülich (Germany); RWTH Aachen Univ. (Germany)

In this study, a series of novel uranyl borates, K4Sr4[(UO2)13(B2O5)2(BO3)2O12], A6[(UO2)12(BO3)8O3](H2O)6 (A = Rb and Cs), and Rb3[(UO2)3(BO3)2O(OH)](H2O), were synthesized using conventional conditions. Among them, K4Sr4[(UO2)13(B2O5)2(BO3)2O12] and A6[(UO2)12(BO3)8O3](H2O)6 were obtained through a high-temperature solid-state reaction method, whereas Rb3[(UO2)3(BO3)2O(OH)](H2O) was synthesized via a hydrothermal reaction. All compounds adopt novel two-dimensional (2D) layered structures in which basic building units (BBUs) consist of corner- or edge-sharing UOx (x = 6, 7 and 8) polyhedra linked with planar BO3 triangles or B2O5 dimers. K4Sr4[(UO2)13(B2O5)2(BO3)2O12] is the first mixed alkali–alkaline earth metal uranyl borate. This compound has the most complex 2D anion topology observed thus far in 2D uranyl borates. The fundamental building block (FBB) in this structure, [(UO2)13(B2O5)2(BO3)2O12]12–, consists of 3 UO8 hexagonal bipyramids and 10 UO7 pentagonal bipyramids connected with 2 BO3 triangles and 2 B2O5 dimers. The FBB of Rb6[(UO2)12(BO3)8O3](H2O)6 is [(UO2)6(BO3)4O3]6–, comprised of five edge-sharing UO7 pentagonal bipyramids, one UO6 tetragonal bipyramid, and four BO3 triangles. The simplest FBB, [(UO2)3(BO3)2O2]4–, occurs in Rb3[(UO2)3(BO3)2O(OH)](H2O), where three UO7 pentagonal bipyramids are linked with two BO3 triangles via edge sharing. The aforementioned FBBs are further polymerized into the corresponding infinite uranyl borates layers. Finally, the synthetic methods, novel topologies, thermal stability, and spectroscopic properties of these compounds are reported herein.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016568
OSTI ID:
1470218
Journal Information:
Crystal Growth and Design, Vol. 17, Issue 11; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (48)

Recent development of metal borate halides: Crystal chemistry and application in second-order NLO materials journal September 2016
Evaluation of f-element borate chemistry journal September 2016
Crystal structures and second-order NLO properties of borogermanates journal November 2012
New Developments in the Synthesis, Structure, and Applications of Borophosphates and Metalloborophosphates journal March 2016
Structural Chemistry of Borophosphates, Metalloborophosphates, and Related Compounds journal August 2007
Lattice dynamics and a magnetic-structural phase transition in the nickel orthoborate N i 3 ( B O 3 ) 2 journal April 2016
PbCd 2 B 6 O 12 and EuZnB 5 O 10 : syntheses, crystal structures and characterizations of two new mixed metal borates journal January 2014
Rare earth separations by selective borate crystallization journal March 2017
Borate Materials in Nonlinear Optics journal September 1998
Design and synthesis of an ultraviolet-transparent nonlinear optical crystal Sr2Be2B2O7 journal January 1995
Se 2 (B 2 O 7 ):  A New Type of Second-Order NLO Material journal June 2006
K 3 B 3 O 4 (OH) 4 ·2H 2 O: A UV Nonlinear Optical Crystal with Isolated [B 3 O 4 (OH) 4 ] 3– Anion Groups journal August 2016
Phase relations in the ternary system SrO–TiO2–B2O3 journal August 2001
Novel Rare Earth Polyborates. 2. Syntheses and Structures journal June 2003
β-RE 1– x Bi x B 3 O 6 (RE = Sm, Eu, Gd, Tb, Dy, Ho, Er, Y): Bi 3+ Substitution Induced Formation of Metastable Rare Earth Borates at Ambient Pressure journal August 2016
Synthesis, crystal structure and characterizations of a new red phosphor K 3 EuB 6 O 12 journal October 2016
SrGe 2 B 2 O 8 and Sr 3 Ge 2 B 6 O 16 : Novel Strontium Borogermanates with Three-Dimensional and Layered Anionic Architectures journal November 2013
Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of A CsP 2 Se 8 ( A = K, Rb, Cs) journal March 2016
Li 3 Cs 2 M 2 B 3 P 6 O 24 (M = Pb, Sr): borophosphates with double six-membered ring of [BP 2 O 8 ] 3− journal January 2016
NaBa 4 (GaB 4 O 9 ) 2 X 3 (X = Cl, Br) with NLO-Active GaO 4 Tetrahedral Unit: Experimental and ab Initio Studies journal March 2016
Ln 2 Ga[B 3 O 6 (OH)] 2 [B 7 O 9 (OH) 2 ](CH 3 CO 2 ) 2 (Ln = Y, Sm, Eu, Gd, Dy): A Series of Lanthanide Galloborates Decorated by Acetate Anions journal June 2016
Recent progress in actinide borate chemistry journal January 2011
Polarity and Chirality in Uranyl Borates: Insights into Understanding the Vitrification of Nuclear Waste and the Development of Nonlinear Optical Materials journal March 2010
Cs 2 USi 6 O 15 : A Tetravalent Uranium Silicate journal July 2011
Hexapotassium (cyclo-octahydroxotetracosaoxohexadecarborato)dioxouranate(VI) dodecahydrate, K6[UO2{B16O24(OH)8}].12H2O journal May 1985
Structure du borate d`uranium UB2O6 journal November 1987
How are Centrosymmetric and Noncentrosymmetric Structures Achieved in Uranyl Borates? journal March 2010
Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates journal March 2011
High-Pressure Synthesis and Characterization of New Actinide Borates, An B 4 O 8 ( An =Th, U) journal October 2013
Synthèse et structure du diborouranate de magnésium, MgB2UO7 journal December 1987
A new low temperature route to uranyl borates with structural variations journal January 2013
Structure−Property Relationships in Lithium, Silver, and Cesium Uranyl Borates journal November 2010
Crystal Chemistry of the Potassium and Rubidium Uranyl Borate Families Derived from Boric Acid Fluxes journal July 2010
Potassium uranyl borate 3D framework compound resulted from temperature directed hydroborate condensation: structure, spectroscopy, and dissolution studies journal January 2016
High Structural Complexity of Potassium Uranyl Borates Derived from High-Temperature/High-Pressure Reactions journal April 2013
Synthèse et structure du borouranate de calcium: CaB2U2O10 journal July 1987
Influence of Synthetic Conditions on Chemistry and Structural Properties of Alkaline Earth Uranyl Borates journal September 2016
Further Evidence for the Stabilization of U(V) within a Tetraoxo Core journal May 2014
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
Rubidium uranyl phosphates and arsenates with polymeric tetrahedral anions: Syntheses and structures of Rb4[(UO2)6(P2O7)4(H2O)], Rb2[(UO2)3(P2O7)(P4O12)] and Rb[(UO2)2(As3O10)] journal August 2009
Underlying nets in three-periodic coordination polymers: topology, taxonomy and prediction from a computer-aided analysis of the Cambridge Structural Database journal January 2011
Vertex-, face-, point-, Schläfli-, and Delaney-symbols in nets, polyhedra and tilings: recommended terminology journal January 2010
A new barium uranyl oxide hydrate mineral, protasite journal March 1986
Structure de la roubaultite, Cu2(UO2)3(CO3)2O2(OH)2.4H2O journal May 1985
Kinetics vs. thermodynamics: a unique crystal transformation from a uranyl peroxo-nanocluster to a nanoclustered uranyl polyborate journal January 2014
Porous Uranyl Borophosphates with Unique Three-Dimensional Open-Framework Structures journal July 2017
Bond length-Raman frequency correlations in borate crystals journal November 1991

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