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RESEARCH PAPER · The Canadian Mineralogist · 2008

NEPTUNYL COMPOUNDS: POLYHEDRON GEOMETRIES, BOND-VALENCE PARAMETERS, AND STRUCTURAL HIERARCHY

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NEPTUNYL COMPOUNDS: POLYHEDRON GEOMETRIES, BOND-VALENCE PARAMETERS, AND STRUCTURAL HIERARCHYOriginalQuaternary Neptunium Compounds: Syntheses and Characterization of KCuNpS3, RbCuNpS3, CsCuNpS3, KAgNpS3, and CsAgNpS322Further insights into intermediate- and mixed-valency in neptunium oxoanion compounds: structure and absorption spectroscopy of K2[(NpO2)3B10O16(OH)2(NO3)2]52Hydrothermal Synthesis and Crystal Structures of Actinide Compounds2Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage74Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage8Crystal and Electronic Structure of a Mixed-Valent Np(IV)−Np(V) Compound: [BuMeIm]5[Np(NpO2)3(H2O)6Cl12]30Incorporation of Neptunium(V) and Iodate into a Uranyl Phosphate: Implications for Mitigating the Release of 237Np and 129I in Repositories23From extended solids to nano-scale actinide clusters25Boronic Acid Flux Synthesis and Crystal Growth of Uranium and Neptunium Boronates and Borates: A Low-Temperature Route to the First Neptunium(V) Borate41Advances in actinide solid-state and coordination chemistry37Recent progress in actinide borate chemistry94Nanoscale uranium-based cage clusters inspired by uranium mineralogy88Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates56U(VI) Uranyl Cation−Cation Interactions in Framework Germanates47Np-incorporation into uranyl phases: A quantum–mechanical evaluation22Cation–Cation Interactions: Crystal Structures of Neptunyl(V) Selenate Hydrates, (NpO2)2(SeO4)(H2O)n (n = 1, 2, and 4)36K(NpO2)3(H2O)Cl4: A Channel Structure Assembled by Two- and Three-Center Cation–Cation Interactions of Neptunyl Cations23Two New Neptunyl(V) Selenites: A Novel Cation–Cation Interaction Framework in (NpO2)3(OH)(SeO3)(H2O)2·H2O and a Uranophane-Type Sheet in Na(NpO2)(SeO3)(H2O)29New Neptunium(V) Borates That Exhibit the Alexandrite Effect20Stabilising pentavalent actinides—visible–near infrared and X-ray absorption spectroscopic studies of the utility of the [(Np 3 W 4 O 15 )(H 2 O) 3 (MW 9 O 33 ) 3 ] 18 − (M = Sb, Bi) structural type13Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism35Preparation, Stability, and Structural Characterization of Plutonium(VII) in Alkaline Aqueous Solution41(UO2)2[UO4(trz)2](OH)2: A U(VI) Coordination Intermediate between a Tetraoxido Core and a Uranyl Ion with Cation–Cation Interactions43Cation–Cation Interactions between Neptunyl(VI) Units24Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems10One-Dimensional Uranyl-2,2′-bipyridine Coordination Polymer with Cation–Cation Interactions: (UO2)2(2,2′-bpy)(CH3CO2)(O)(OH)44Incorporation of Neptunium(VI) into a Uranyl Selenite14Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges344Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products372New Reactivity of the Uranyl(VI) Ion116Synthetic Influences on Neptunium Incorporation in Naturally Occurring Copper Uranyl Phosphates11Transuranium Inorganic Chemistry4Synthesis and Characterization of the First 2 D Neptunyl Structure Stabilized by Side‐on Cation–Cation Interactions23Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings24Crystal growth, structural characterization, cation–cation interaction classification, and optical properties of uranium( vi ) containing oxychlorides, A 4 U 5 O 16 Cl 2 (A = K, Rb), Cs 5 U 7 O 22 Cl 3 , and AUO 3 Cl (A = Rb, Cs)27Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates17Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials15Incorporation of Np(V) and U(VI) in carbonate and sulfate minerals crystallized from aqueous solution26Structural and Morphological Influences on Neptunium Incorporation in Uranyl Molybdates1A Revised and Expanded Structure Hierarchy of Natural and Synthetic Hexavalent Uranium Compounds172Oxo Clusters of 5f Elements24Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation19Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies18Evaluation of f-element borate chemistry76A first principles study of energetics and electronic structural responses of uranium-based coordination polymers to Np incorporation5Synthesis and Study of the First Zeolitic Uranium Borate22A neptunium( v )-mediated interwoven transuranium-rotaxane network incorporating a mechanically interlocked [ c 2]daisy chain unit25Impacts of Oxo Interactions on Np(V) Crown Ether Complexes19Mixed-Valent Cyanoplatinates Featuring Neptunyl–Neptunyl Cation–Cation Interactions6Actinides: Crystallography0Rb2[Ca(NpO2)2(PO4)2], the First Mixed Alkali–Alkaline Earth Metals Neptunyl(V) Phosphate: Crystal Chemistry and Sheet Stereoisomerism7Actinyl-cation interactions: experimental and theoretical assessment of [Np( vi )O 2 Cl 4 ] 2− and [U( vi )O 2 Cl 4 ] 2− systems27Mixed-valent neptunium oligomer complexes based on cation–cation interactions4A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds9Structural Evolution in the Rare-Earth Uranyl Vanadates Ln2[(UO2)2V2O8]3·nH2O, Singularity of the Lanthanum Compound, and Single-Crystal to Single-Crystal Partial Dehydration7Thermochemical study of tetravalent metal sulfate tetrahydrates: A4+(SO4)2(H2O)4 (A4+ = Zr, Ce, U)4Determination of complex formation constants of neptunium(V) with propionate and lactate in 0.5–2.6 m NaCl solutions at 22–60°C using a solvent extraction technique2In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal–Organic Framework47Quantum-mechanical determination of the incorporation of pentavalent plutonium into carbonate and sulfate minerals6Hydrated Uranium Oxides3Insights into the Structural Chemistry of Anhydrous and Hydrous Hexavalent Uranium and Neptunium Dinitrato, Trinitrato, and Tetranitrato Complexes16Molecular oxides of high-valent actinides18Effects of ageing on the occurrence form of uranium in vertical soil layers near an uranium tailing reservoir2The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds41Unusual Metal–Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry32Electronic Structures and Unusual Chemical Bonding in Actinyl Peroxide Dimers [An2O6]2+ and [(An2O6)(12-crown-4 ether)2]2+ (An = U, Np, and Pu)4Density Functional Theory Guided Investigation of Ligand‐Induced Neptunyl‐Neptunyl Interactions5Modularity, polytypism, topology, and complexity of crystal structures of inorganic compounds (Review)32Cation-cation interaction in Np(V) o-chlorobenzoate complexes with 1,10-phenanthroline and 2,2′-bipyridine3Hydrothermal synthesis and structure of organically templated layered neptunyl( vi ) phosphate (NpO 2 ) 3 (PO 4 ) 2 (Terpy)0Improving Understanding of Npo2 and Np2o5 Through Vibrational Spectroscopy0Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks6Improving understanding of NpO2 and Np2O5 through vibrational spectroscopy11How novel is protactinium: Insights into the structure and properties of (PaO) 2 (SO 4 ) 3 (H 2 O) 21Cation–Cation Interactions in Neptunium(V,VI)-diglycolamide System0Breaking the Neptunyl Barrier: Direct Access to Neptunium(IV) in Aqueous Solution via Polyoxometalate-Mediated Reduction and Stabilization9The first bimetallic Np( v ) MOF with a Np 4 Cs 2 O 8 structural unit: sorption properties and thermal and radiation stability0

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  1. Quaternary Neptunium Compounds: Syntheses and Characterization of KCuNpS3, RbCuNpS3, CsCuNpS3, KAgNpS3, and CsAgNpS3

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  2. Further insights into intermediate- and mixed-valency in neptunium oxoanion compounds: structure and absorption spectroscopy of K2[(NpO2)3B10O16(OH)2(NO3)2]

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  3. Hydrothermal Synthesis and Crystal Structures of Actinide Compounds

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  4. Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage

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  5. Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage

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  6. Crystal and Electronic Structure of a Mixed-Valent Np(IV)−Np(V) Compound: [BuMeIm]5[Np(NpO2)3(H2O)6Cl12]

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  7. Incorporation of Neptunium(V) and Iodate into a Uranyl Phosphate: Implications for Mitigating the Release of 237Np and 129I in Repositories

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  8. From extended solids to nano-scale actinide clusters

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  9. Boronic Acid Flux Synthesis and Crystal Growth of Uranium and Neptunium Boronates and Borates: A Low-Temperature Route to the First Neptunium(V) Borate

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  12. Nanoscale uranium-based cage clusters inspired by uranium mineralogy

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  13. Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates

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  14. U(VI) Uranyl Cation−Cation Interactions in Framework Germanates

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  15. Np-incorporation into uranyl phases: A quantum–mechanical evaluation

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  16. Cation–Cation Interactions: Crystal Structures of Neptunyl(V) Selenate Hydrates, (NpO2)2(SeO4)(H2O)n (n = 1, 2, and 4)

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    Geng Bang Jin, S. Skanthakumar, L. Soderholm

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  17. K(NpO2)3(H2O)Cl4: A Channel Structure Assembled by Two- and Three-Center Cation–Cation Interactions of Neptunyl Cations

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    Shuao Wang, Evgeny V. Alekseev, Wulf Depmeier, Thomas E. Albrecht‐Schmitt

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  18. Two New Neptunyl(V) Selenites: A Novel Cation–Cation Interaction Framework in (NpO2)3(OH)(SeO3)(H2O)2·H2O and a Uranophane-Type Sheet in Na(NpO2)(SeO3)(H2O)

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  19. New Neptunium(V) Borates That Exhibit the Alexandrite Effect

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  20. Stabilising pentavalent actinides—visible–near infrared and X-ray absorption spectroscopic studies of the utility of the [(Np 3 W 4 O 15 )(H 2 O) 3 (MW 9 O 33 ) 3 ] 18 − (M = Sb, Bi) structural type

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  21. Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism

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  22. Preparation, Stability, and Structural Characterization of Plutonium(VII) in Alkaline Aqueous Solution

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  23. (UO2)2[UO4(trz)2](OH)2: A U(VI) Coordination Intermediate between a Tetraoxido Core and a Uranyl Ion with Cation–Cation Interactions

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  25. Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems

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  30. New Reactivity of the Uranyl(VI) Ion

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  31. Synthetic Influences on Neptunium Incorporation in Naturally Occurring Copper Uranyl Phosphates

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  33. Synthesis and Characterization of the First 2 D Neptunyl Structure Stabilized by Side‐on Cation–Cation Interactions

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  34. Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings

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  35. Crystal growth, structural characterization, cation–cation interaction classification, and optical properties of uranium( vi ) containing oxychlorides, A 4 U 5 O 16 Cl 2 (A = K, Rb), Cs 5 U 7 O 22 Cl 3 , and AUO 3 Cl (A = Rb, Cs)

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  36. Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

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  37. Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials

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  38. Incorporation of Np(V) and U(VI) in carbonate and sulfate minerals crystallized from aqueous solution

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  39. Structural and Morphological Influences on Neptunium Incorporation in Uranyl Molybdates

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  40. A Revised and Expanded Structure Hierarchy of Natural and Synthetic Hexavalent Uranium Compounds

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  41. Oxo Clusters of 5f Elements

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  42. Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation

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  43. Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies

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  44. Evaluation of f-element borate chemistry

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  45. A first principles study of energetics and electronic structural responses of uranium-based coordination polymers to Np incorporation

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  46. Synthesis and Study of the First Zeolitic Uranium Borate

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  47. A neptunium( v )-mediated interwoven transuranium-rotaxane network incorporating a mechanically interlocked [ c 2]daisy chain unit

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  48. Impacts of Oxo Interactions on Np(V) Crown Ether Complexes

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  49. Mixed-Valent Cyanoplatinates Featuring Neptunyl–Neptunyl Cation–Cation Interactions

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  50. Actinides: Crystallography

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