The potential of palladacycles: more than just precatalysts

Ferroelectric Metal–Organic Frameworks

Polynuclear NiII and MnII azido bridging complexes. Structural trends and magnetic behavior

Zero-field splitting in metal complexes

1. Scope of Article and Previous Related Reviews 5346 2. Introduction 5346 2.1. Destruction 5347 2.2. Sensing 5347 2.3. Historical Context 5348 2.3.1. Brief History and Molecular Structure 5348 2.4. Related Compounds and Nomenclature 5348 2.4.1. Phosphorus(V) Parent Compounds and Fundamental Chemistry 5348 2.4.2. Pesticides 5349 2.4.3. Simulants 5349 2.4.4. Decomposition Products 5350 2.5. Toxicology 5351 2.5.1. Acetylcholine Esterase (AChE) Inhibition 5351 2.5.2. Endocannabinoid System Activation 5352 2.6. Critical Needs To Decontaminate and Detect 5353 2.7. Treaties and Conventions 5354 3. Stockpile Destruction 5355 3.1. Agent Storage 5355 3.2. Protection Protocols and Logistics 5355 3.3. Background 5355 3.4. Methods Currently Employed 5355 3.4.1. Incineration 5355 3.4.2. Neutralization by Base Hydrolysis 5356 4. Decomposition Reactions 5357 4.1. Hydrolysis 5357 4.2. Autocatalytic Hydrolysis or Hydrolysis Byproducts 5358 4.3. Use of Peroxide 5359 4.4. Oxidation with Bleach and Related Reagents 5360 4.5. Alkoxide as Nucleophile 5360 4.5.1. Basic Media 5360 4.5.2. Metal-Catalyzed Reactions 5361 4.5.3. Metal-Assisted Reactions 5363 4.5.4. Biotechnological Degradation 5363 4.5.5. Cyclodextrin-Assisted Reactions 5370 4.6. Halogen as the Nucleophile 5370 4.6.1. Use of BrOx 5370 4.6.2. Use of Other Halogens 5371 4.6.3. Use of Group 13 Chelates 5371 4.7. Surface Chemistry 5371 4.7.1. Bare Metals and Solid Nanoparticles 5371 4.7.2. Metal Oxides 5371 4.7.3. Representative Elements 5372 4.7.4. d-Block (Groups 4 10) 5373 4.7.5. Solid Metal Oxides of Group 3 and the Lanthanides 5375 4.7.6. Porous Silicon and Related Systems 5375 4.7.7. Zeolites 5375 4.7.8. Comparative IR Data 5375 4.8. Other Types of Systems 5375 5. Decontamination 5376 5.1. Overview: Ability to React with All Types of Agents, Ease of Application, and Compatibility with Treated Objects 5376 6. Agent Fate and Disposal 5378 6.1. Indoor 5378 6.2. Concrete and Construction Surfaces 5378 6.3. Landfills 5379 7. Sensing and Detection 5379 7.1. Possible Metal Ion Binding Modes in Solution 5379 7.1.1. Early Reports of Phosph(on)ate [R3PdO 3 3 3M nþ] Interactions (R= Alkyl, Alkoxyl) 5380 7.1.2. Coordination Chemistry of Downstream Non-P-Containing Products of Decomposition 5380 7.2. Colorimetric Detection 5381 7.3. Chemiluminescence: Fluorescence and Phosphorescence 5382 7.3.1. Lanthanide-Based Catalysts 5382 7.3.2. Organometallic-Based Sensors 5382 7.3.3. Organic Design 5382 7.3.4. Biologically-Based Luminescence Detection 5382 7.3.5. Polymer and Bead Supports 5382 7.4. Porous Silicon 5383 7.5. Carbon Nanotubes 5383

Destruction and Detection of Chemical Warfare Agents

)2 single crystals doped with Er3+ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) A, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er3+ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C2 symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the 4F7/2 multiplet. The Judd–Ofelt (JO) parameters of Er3+ in KGW have been calculated: Ω2=8.90×10-20 cm2, Ω4=0.96×10-20 cm2, Ω6=0.82×10-20 cm2. Lifetimes of the 4S3/2, 4F9/2, and 4I11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the 4S3/2 and 4I11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes.

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Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

The crystal structure of monoclinic KGd(WO4)2 (KGW) has been refined at room temperature by using single-crystal X-ray diffraction data. The unit-cell parameters are a = 10.652 (4), b = 10.374 (6), c = 7.582 (2) A, β = 130.80 (2)°, with Z = 4, in space group C2/c. The linear thermal expansion tensor has been determined and the principal axes are [302], [010] and [106]. The principal axis with maximum thermal expansion (\boldalpha'_{33} = 23.44 × 10−6 K−1), {\bf X}'_{3}, was located 12° from the c axis. Undoped crystals of KGW and crystals that were partially doped by Pr, Nd, Ho, Er, Tm and Yb were grown by the top-seeding-solution growth slow-cooling method. The effect of doping on the KGW structure was observed in the cell parameters and in morphological changes. The changes in parameters follow the changes in lanthanide ionic radii. The doped crystals show {021} and {\bar{2}21} faces in addition to the {110}, {\bar{1}11}, {010}, {130} and {310} faces which basically follow the habit of the undoped KGW crystals. The development of the faces is related to the number of the most important periodic bond chains parallel to them.

Structural study of monoclinic KGd(WO4)2 and effects of lanthanide substitution

Crystal structure and magnetic properties of [Ni(terpy)(N3)2]2·2H2O, a nickel(II) dinuclear complex with ferromagnetic interaction

The crystal structure of monoclinic KLu(WO4)2 (KLuW) crystals was determined at room temperature by using single-crystal X-ray diffraction data. The unit-cell parameters were a = 10.576 (7), b = 10.214 (7), c = 7.487 (2) A, β = 130.68 (4)°, with Z = 4, in space group C2/c. The unit-cell parameters of KLu1−xYbx(WO4)2 were determined in relation to Yb concentration. Vickers micro-indentations were used to study the microhardness of KLuW. The linear thermal expansion tensor was determined and the principal axis with maximum thermal expansion (\alpha_{33}' = 16.72 × 10−6 K−1), X_3', was located 13.51° from the c axis. The room-temperature optical tensor was studied in the near-infrared (NIR) and visible range. The principal optical axis with maximum refractive index (ng = 2.113), Ng, was located 18.5° from the c axis at 632.8 nm. Undoped and ytterbium-doped KLuW crystals were grown by the TSSG (top-seeded-solution growth) slow-cooling method. The crystals show {110}, {\bar{1}11}, {010} and {310} faces that basically constitue the habit of the KLuW crystals.

Structural redetermination, thermal expansion and refractive indices of KLu(WO4)2

The crystal structure of monoclinic KYb(WO4)2 (KYbW) crystals has been refined (in space group C2/c) at room temperature by using single-crystal X-ray diffraction data. KYbW undoped crystals were grown by the TSSG (top-seeded-solution growth) slow-cooling method. The crystals show {110}, {\bar{1}11}, {010} and {310} faces, which basically define their habit. The linear thermal expansion tensor has been determined and the principal axis with maximum thermal expansion (\alpha ^{\,\prime}_{33} = 16.68 × 10−6 K−1), {\bf X}^{\,\prime}_{3}, was located 12° from the c axis. Its principal {\bf X}^{\,\prime}_{1}, {\bf X}^{\,\prime}_{2} and {\bf X}^{\,\prime}_{3} axes are [302], [010] and [106] directions, respectively, in the crystallographic system. The optical tensor has been studied at λ = 632.8 nm at room temperature; two principal axes, Ng and Nm, are located in the ac plane, while the other, Np, is parallel to [010]. The principal axis with maximum refractive index (ng = 2.45), Ng, was located 19° from the c axis.

X. Solans

Papers

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

Structural study of monoclinic KGd(WO4)2 and effects of lanthanide substitution

Crystal structure and magnetic properties of [Ni(terpy)(N3)2]2·2H2O, a nickel(II) dinuclear complex with ferromagnetic interaction

Structural redetermination, thermal expansion and refractive indices of KLu(WO4)2

Structure, crystal growth and physical anisotropy of KYb(WO4)2, a new laser matrix