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RESEARCH PAPER · Chemical Reviews · 2012

Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid-State Structures

Michael B. Andrews, Christopher L. Cahill

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Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid-State StructuresOriginalSolution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products372Metal–organic hybrids involving the [UO 2 Cl 3 (NO 3 )] 2− tecton and the role of halogen polarizability28New Reactivity of the Uranyl(VI) Ion116Sulfonate Complexes of Actinide Ions: Structural Diversity in Uranyl Complexes with 2-Sulfobenzoate71An exploration of homo- and heterometallic UO 2 2+ hybrid materials containing chelidamic acid: synthesis, structure, and luminescence studies32Chiral uranyl-organic compounds assembled with achiral furandicarboxylic acid by spontaneous resolution45One- to three-dimensional uranyl–organic assemblies with 3-sulfophthalic and 5-sulfoisophthalic acids29Recent developments in actinide–ligand multiple bonding322Uranyl–3d block metal ion heterometallic carboxylate complexes including additional chelating nitrogen donors37Uranyl–copper(ii) heterometallic oxalate complexes: coordination polymers and frameworks47From Order to Disorder and Back Again: In Situ Hydrothermal Redox Reactions of Uranium Phosphites and Phosphates28Synthesis, Structures, and Luminescent Properties of Uranyl Terpyridine Aromatic Carboxylate Coordination Polymers85ChemInform Abstract: Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid‐State Structures0Two Systems of [DabcoH2]2+/[PipH2]2+–Uranyl–Oxalate Showing Reversible Crystal-to-Crystal Transformations Controlled by the Diammonium/Uranyl/Oxalate Ratios in Aqueous Solutions ([DabcoH2]2+ = 1,4-Diazabicyclo-[2.2.2]-octaneH2 and [PipH2]2+ = PiperazineH2)23Syntheses, structures and luminescent properties of two organic templated uranyl phosphonates18Uranyl complex with phenolate–sulphonate and diphenyldiazenecarbohydrazonate ligands4Two new 2p–3d–4f heterometallic coordination polymers based on 3,5-pyrazoledicarboxylic acid: synthesis, crystal structures and magnetic properties9A Uranyl Hybrid Compound Designed from Urea‐Bearing Dipropionic Acid16Mixed Formate-Dicarboxylate Coordination Polymers with Tetravalent Uranium: Occurrence of Tetranuclear {U4O4} and Hexanuclear {U6O4(OH)4} Motifs662,2′‐Bipyridine and 1,10‐Phenanthroline as Coligands or Structure‐Directing Agents in Uranyl–Organic Assemblies with Polycarboxylic Acids56Series of Uranyl-4,4′-biphenyldicarboxylates and an Occurrence of a Cation–Cation Interaction: Hydrothermal Synthesis and in Situ Raman Studies36Supramolecular architectures and structural diversity in a series of lead (II) Chelates involving 5-Chloro/Bromo thiophene-2-carboxylate and N,N’-donor ligands13Porphyrin‐POSS Molecular Hybrids22Actinide oxalates, solid state structures and applications160The crystal chemistry of uranium carboxylates394Isolation of thorium benzoate polytypes with discrete ThO8 square antiprismatic units involved in chain-like assemblies16Spectroscopic Studies and Crystal Structures of Double Thorium(IV) Oxalates with Sodium Ions15Molecular and Polymeric Uranyl and Thorium Complexes with Sulfonate‐Containing Ligands33Supramolecular Interactions in PuO2Cl42– and PuCl62– Complexes with Protonated Pyridines: Synthesis, Crystal Structures, and Raman Spectroscopy33Uranyl(VI) Complexes in and from Imidazolium Acetate Ionic Liquids: Carbenes versus Acetates?35Chiral one- to three-dimensional uranyl–organic assemblies from (1R,3S)-(+)-camphoric acid47Isolation of a series of uranium organophosphinates11MOFs of Uranium and the Actinides95Self-assembly and magnetic properties of Ni( ii )/Co( ii ) coordination polymers based on 1,4-bis(imidazol-1-yl)benzene and varying biphenyltetracarboxylates38Metal-organic frameworks based on uranyl and phosphonate ligands15Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials39Uranyl–Organic Frameworks with Polycarboxylates: Unusual Effects of a Coordinating Solvent77Crystal Chemistry of Uranyl Carboxylate Coordination Networks Obtained in the Presence of Organic Amine Molecules60A Highly Adjustable Coordination System: Nanotubular and Molecular Cage Species in Uranyl Ion Complexes with Kemp’s Triacid46Postsynthetic Rearrangement/Metalation as a Route to Bimetallic Uranyl Coordination Polymers: Syntheses, Structures, and Luminescence70Synthesis and characterization of 1-D uranyl thiodigycolate coordination polymers10Room temperature crystallization of trichlorodioxouranate [UO2Cl3(L)] species in molecular assemblies involving aliphatic dicarboxylate linkers18Poly[diammonium [diaqua(μ7-benzene-1,2,3,4,5,6-hexacarboxylato)tetraoxidodiuranium(VI)]]8Synthesis, crystal structure and spectroscopic studies of some organic/inorganic hybrid materials containing isostructural monomeric uranyl complexes bridged by bipyridyl typed ligands16Activation of Small Molecules by Molecular Uranium Complexes119Increasing Complexity in the Uranyl Ion–Kemp’s Triacid System: From One- and Two-Dimensional Polymers to Uranyl–Copper(II) Dodeca- and Hexadecanuclear Species47A Family of UO22+–5-Nitro-1,3-dicarboxylate Hybrid Materials: Structural Variation As a Function of pH and Structure Directing Species20A new organically templated open-framework uranyl ethylenediphosphonate6Visible‐Light‐Driven, Tunable, Photoelectrochemical Performance of a Series of Metal‐Chelate, Dye‐Organized, Crystalline, CdS Nanoclusters27Organothorium complexes containing terminal metal-ligand multiple bonds53The influence of pressure on the structure of a 2D uranium(VI) carboxyphosphonoate compound11Challenging conventional f-element separation chemistry – reversing uranyl( vi )/lanthanide( iii ) solvent extraction selectivity14Syntheses and characterization of two novel tetranuclear lead(II) clusters self-assembled by hydrogen bonded interactions6Photocatalytic Application of 4f–5f Inorganic–Organic Frameworks: Influence of Lanthanide Contraction on the Structure and Functional Properties of a Series of Uranyl–Lanthanide Complexes34Straightforward Reductive Routes to Air-Stable Uranium(III) and Neptunium(III) Materials15CuPYDC Metalloligands and Postsynthetic Rearrangement/Metalation as Routes to Bimetallic Uranyl Containing Hybrid Materials: Syntheses, Structures, and Fluorescence37Uranyl Ion Complexes with all-cis-1,3,5-Cyclohexanetricarboxylate: Unexpected Framework and Nanotubular Assemblies55Copper(I) and Copper(II) Uranyl Heterometallic Hybrid Materials49Four new dinuclear uranyl complexes based on p- and m-toluic acid: Syntheses, structures, luminescent and photocatalytic properties21[(C 2 H 5 ) 4 N][U 2 O 4 (HCOO) 5 ], an Ammonium Uranyl Formate Framework Showing Para- to Ferro-Electric Transition: Synthesis, Structures, and Properties17Two new two-dimensional layered uranyl-bearing polycarboxylates from semi-rigid tetracarboxylic acids15Uranyl Ion Complexes with trans‐3‐(3‐Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework21The First Family of Actinide Carboxyphosphinates: Two‐ and Three‐Dimensional Uranyl Coordination Polymers27Novel [(UO2)O6(NO3) ] (n= 1, 2) based units in organically templated uranyl compounds10Isolated Uranyl Chromate and Polychromate Units in Crown Ether Templated Compounds18Coordination polymers of uranium( iv ) terephthalates42Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts27Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions20Synthesis of surface ion-imprinted magnetic microspheres by locating polymerization for rapid and selective separation of uranium( vi )50Incorporating Guest Molecules into Honeycomb Structures Constructed from Uranium(VI)-Polycarboxylates: Structural Diversities and Photocatalytic Activities for the Degradation of Organic Dye91Complexation of uranyl ions by N-(sulfoethyl)-iminodiacetic acid: Hydrothermal synthesis, luminescence, and uranyl sequestration1Combining coordination and supramolecular chemistry to explore uranyl assembly in the solid state51A family of 3D UO 2 2+ –5-X-1,3-dicarboxylate (X = –H, –NO 2 , –NH 2 , –OH) hybrid materials: structural relevance with variation of substituent groups and photochemical properties29Design and synthesis of a chiral uranium-based microporous metal organic framework with high SHG efficiency and sequestration potential for low-valent actinides58Homochiral 3D coordination polymer with unprecedented three-directional helical topology from achiral precursor: synthesis, crystal structure, and luminescence properties of uranyl succinate metal–organic framework24Hybrid Materials of the f-Elements Part I5Hybrid Materials of the f-Elements Part II5Solvent effects in solvo-hydrothermal synthesis of uranyl ion complexes with 1,3-adamantanediacetate33Synthetic, structural, and luminescence study of uranyl coordination polymers containing chelating terpyridine and trispyridyltriazine ligands34Two novel uranyl complexes of a semi-rigid aromatic tetracarboxylic acid supported by an organic base as an auxiliary ligand or a templating agent: an experimental and theoretical exploration16Uranium( vi ) complexes with isonicotinic acid: from monomer to 2D polymer with unique U–N bonding43Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence32Thorium Terephthalates Coordination Polymers Synthesized in Solvothermal DMF/H2O System143Uranyl and Uranyl–3d Block Cation Complexes with 1,3-Adamantanedicarboxylate: Crystal Structures, Luminescence, and Magnetic Properties68Comparison of uranium(VI) and thorium(IV) coordination polymers with p-toluenesulfonic acid16Polypyrrole/Silver Coaxial Nanowire Aero-Sponges for Temperature-Independent Stress Sensing and Stress-Triggered Joule Heating206Heterometallic zinc uranium oxyfluorides incorporating imidazole ligands3Structural variations in terbium(III) complexes with 1,3-adamantanedicarboxylate and diverse co-ligands10Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes20Direct synthesis of carbon-based microtubes by hydrothermal carbonization of microorganism cells13Umbellate Distortions of the Uranyl Coordination Environment Result in a Stable and Porous Polycatenated Framework That Can Effectively Remove Cesium from Aqueous Solutions449Why Is Uranyl Formohydroxamate Red?25Solvothermal Synthesis of Tetravalent Uranium with Isophthalate or Pyromellitate Ligands13Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers53Structural chemistry of uranium phosphonates143Tetranuclear Uranyl Polyrotaxanes: Preferred Selectivity toward Uranyl Tetramer for Stabilizing a Flexible Polyrotaxane Chain Exhibiting Weakened Supramolecular Inclusion28Two-dimensional assemblies in f-element ion (UO22+, Yb3+) complexes with two cyclohexyl-based polycarboxylates21Die Renaissance der nichtwässrigen Uranchemie81The Renaissance of Non‐Aqueous Uranium Chemistry515Uranyl Ion Complexes with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxylic Acid: Structural and Spectroscopic Studies of One- to Three-Dimensional Assemblies36Two Uranyl Complexes with Pyromellitic Acid. A Heterometallic Complex with U=O–CuII Interaction7Unexpected cis-dioxido uranyl carboxylate compound: Synthesis, characterization and photocatalytic activity of uranyl-succinate complexes17CoII, NiII and UO2II complexes with β-diketones and their arylhydrazone derivatives: Synthesis, structure and catalytic activity in Henry reaction16Structural Variations in the Uranyl/4,4′-Biphenyldicarboxylate System. Rare Examples of 2D → 3D Polycatenated Uranyl–Organic Networks78Synthesis, Structure, and Photoluminescence Properties of an Organically‐Templated Uranyl Selenite3Complexes of uranyl glutarate with urea and dimethylurea: Synthesis and structure5Multifunctional Uranyl Hybrid Materials: Structural Diversities as a Function of pH, Luminescence with Potential Nitrobenzene Sensing, and Photoelectric Behavior as p-type Semiconductors56Self-assembly of [UO2X4]2− (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties45Silver Ion-Mediated Heterometallic Three-Fold Interpenetrating Uranyl–Organic Framework52Facile fabrication of magnetic cucurbit[6]uril/graphene oxide composite and application for uranium removal116The templated synthesis of a unique type of tetra-nuclear uranyl-mediated two-fold interpenetrating uranyl–organic framework36Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid28Probing the Influence of N‐Donor Capping Ligands on Supramolecular Assembly in Molecular Uranyl Materials45A family of uranium–carboxylic acid hybrid materials: synthesis, structure and mixed-dye selective adsorption17An investigation of the interactions of Eu 3+ and Am 3+ with uranyl minerals: implications for the storage of spent nuclear fuel21Anchoring flexible uranyl dicarboxylate chains through stacking interactions of ancillary ligands on chiral U( vi ) centres37Counter-ion control of structure in uranyl ion complexes with 2,5-thiophenedicarboxylate39First three-dimensional actinide polyrotaxane framework mediated by windmill-like six-connected oligomeric uranyl: dual roles of the pseudorotaxane precursor19Structural diversity of uranyl acrylates6Uranium(VI) hybrid materials with [(UO 2 ) 3 (µ 3 ‐O)(µ 2 ‐OH) 3 ] + as the sub–building unit via uranyl–cation interactions21Synthesis, structures, and photoluminescent properties of two uranium complexes constructed by a flexible zwitterion ligand18From Helicates to Borromean Links: Chain Length Effect in Uranyl Ion Complexes of Aliphatic α,ω-Dicarboxylates21Synthesis and Crystal Structure Characterization of Thorium Trimesate Coordination Polymers34Directing dimensionality in uranyl malate and copper uranyl malate compounds15Nano-diamond particles functionalized with single/double-arm amide–thiourea ligands for adsorption of metal ions49Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions34UO22+-polycarboxylate heterometallic complexes: structure, spectra, and photocatalytic properties12Structural Variations of the First Family of Heterometallic Uranyl Carboxyphosphinate Assemblies by Synergy between Carboxyphosphinate and Imidazole Ligands21Counterion-Induced Variations in the Dimensionality and Topology of Uranyl Pimelate Complexes41Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer32One-dimensional uranium(VI) coordination polymers with pyridinecarboxylate ligands14Entangled Uranyl Organic Frameworks with (10,3)-b Topology and Polythreading Network: Structure, Luminescence, and Computational Investigation43Uranyl oxamate hydrates: hydrothermal synthesis, crystal structure, photophysical properties, and selective crystallization0First Cationic Uranyl–Organic Framework with Anion-Exchange Capabilities101Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II)46Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2′:6′,2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior63Exploring Crystal Engineering for Porous Uranyl–Organic Frameworks: Insight into Hydrolysis and In Situ Reaction, Structural Variation‐Dependent Physical Properties6An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties17Crystal structures of new uranyl glutarate coordination polymers (NH4)2[(UO2)2(glt)3]·nH2O (n= 3 or 6) and R[UO2(glt)(Hglt)]·H2O (R = Na, K, Rb or Cs)10Uranium–Carbene–Imido Metalla‐Allenes: Ancillary‐Ligand‐Controlled cis‐/trans‐Isomerisation and Assessment of trans Influence in the R2C=UIV=NR′ Unit (R=Ph2PNSiMe3; R′=CPh3)39Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs14Behaviour of complexes of f–elements in the environment – An experimental and theoretical analysis2Hydrothermal Crystallization of Uranyl Coordination Polymers Involving an Imidazolium Dicarboxylate Ligand: Effect of pH on the Nuclearity of Uranyl-Centered Subunits38Structures of Metal–Organic Frameworks with Rod Secondary Building Units909Synthesis and crystal structure analysis of uranyl triple acetates12Series of Hydrated Heterometallic Uranyl-Cobalt(II) Coordination Polymers with Aromatic Polycarboxylate Ligands: Formation of U═O—Co Bonding upon Dehydration Process29Harnessing uranyl oxo atoms via halogen bonding interactions in molecular uranyl materials featuring 2,5-diiodobenzoic acid and N-donor capping ligands39Tetrahydrofurantetracarboxylic Acid: An Isomerizable Framework-Forming Ligand in Homo- and Heterometallic Complexes with UO22+, Ag+, and Pb2+23A Highly Stable 3D Luminescent Indium–Polycarboxylic Framework for the Turn-off Detection of UO22+, Ru3+, and Biomolecule Thiamines60Alkali Halide Cubic Cluster Anions ([Cs8X27]19–, X = Cl, Br) Isolated from Water7

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  2. Metal–organic hybrids involving the [UO 2 Cl 3 (NO 3 )] 2− tecton and the role of halogen polarizability

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  3. New Reactivity of the Uranyl(VI) Ion

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  4. Sulfonate Complexes of Actinide Ions: Structural Diversity in Uranyl Complexes with 2-Sulfobenzoate

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  5. An exploration of homo- and heterometallic UO 2 2+ hybrid materials containing chelidamic acid: synthesis, structure, and luminescence studies

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  6. Chiral uranyl-organic compounds assembled with achiral furandicarboxylic acid by spontaneous resolution

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  8. Recent developments in actinide–ligand multiple bonding

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  11. From Order to Disorder and Back Again: In Situ Hydrothermal Redox Reactions of Uranium Phosphites and Phosphates

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  13. ChemInform Abstract: Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid‐State Structures

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  14. Two Systems of [DabcoH2]2+/[PipH2]2+–Uranyl–Oxalate Showing Reversible Crystal-to-Crystal Transformations Controlled by the Diammonium/Uranyl/Oxalate Ratios in Aqueous Solutions ([DabcoH2]2+ = 1,4-Diazabicyclo-[2.2.2]-octaneH2 and [PipH2]2+ = PiperazineH2)

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  36. Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials

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  37. Uranyl–Organic Frameworks with Polycarboxylates: Unusual Effects of a Coordinating Solvent

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  38. Crystal Chemistry of Uranyl Carboxylate Coordination Networks Obtained in the Presence of Organic Amine Molecules

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  39. A Highly Adjustable Coordination System: Nanotubular and Molecular Cage Species in Uranyl Ion Complexes with Kemp’s Triacid

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  40. Postsynthetic Rearrangement/Metalation as a Route to Bimetallic Uranyl Coordination Polymers: Syntheses, Structures, and Luminescence

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  41. Synthesis and characterization of 1-D uranyl thiodigycolate coordination polymers

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  42. Room temperature crystallization of trichlorodioxouranate [UO2Cl3(L)] species in molecular assemblies involving aliphatic dicarboxylate linkers

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  45. Activation of Small Molecules by Molecular Uranium Complexes

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  47. A Family of UO22+–5-Nitro-1,3-dicarboxylate Hybrid Materials: Structural Variation As a Function of pH and Structure Directing Species

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  48. A new organically templated open-framework uranyl ethylenediphosphonate

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  50. Organothorium complexes containing terminal metal-ligand multiple bonds

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