High pressure synthesis of phosphine from the elements and the discovery of the missing (PH3)2H2 tile.

High pressure reactivity of phosphorus and hydrogen is relevant to fundamental chemistry, energy conversion and storage, and materials science. Here we report the synthesis of (PH3)2H2, a crystalline van der Waals (vdW) compound (I4cm) made of PH3 and H2 molecules, in a Diamond Anvil Cell by direct catalyst-free high pressure (1.2 GPa) and high temperature (T â‰² 1000 K) chemical reaction of black phosphorus and liquid hydrogen, followed by room T compression above 3.5 GPa. Group 15 elements were previously not known to form H2-containing vdW compounds of their molecular hydrides. The observation of (PH3)2H2, identified by synchrotron X-ray diffraction and vibrational spectroscopy (FTIR, Raman), therefore represents the discovery of a previously missing tile, specifically corresponding to P for pnictogens, in the ability of non-metallic elements to form such compounds. Significant chemical implications encompass reactivity of the elements under extreme conditions, with the observation of the P analogue of the Haber-Bosch reaction for N, fundamental bond theory, and predicted high pressure superconductivity in P-H systems.

Nuclear spin coupling crossover in dense molecular hydrogen.

One of the most striking properties of molecular hydrogen is the coupling between molecular rotational properties and nuclear spin orientations, giving rise to the spin isomers ortho- and para-hydrogen. At high pressure, as intermolecular interactions increase significantly, the free rotation of H2 molecules is increasingly hindered, and consequently a modification of the coupling between molecular rotational properties and the nuclear spin system can be anticipated. To date, high-pressure experimental methods have not been able to observe nuclear spin states at pressures approaching 100 GPa (Meier, Annu. Rep. NMR Spectrosc. 94:1-74, 2017; Meier, Prog. Nucl. Magn. Reson. Spectrosc. 106-107:26-36, 2018) and consequently the effect of high pressure on the nuclear spin statistics could not be directly measured. Here, we present in-situ high-pressure nuclear magnetic resonance data on molecular hydrogen in its hexagonal phase I up to 123 GPa at room temperature. While our measurements confirm the presence of ortho-hydrogen at low pressures, above 70 GPa, we observe a crossover in the nuclear spin statistics from a spin-1 quadrupolar to a spin-1/2 dipolar system, evidencing the loss of spin isomer distinction. These observations represent a unique case of a nuclear spin crossover phenomenon in quantum solids.

A versatile diamond anvil cell for X-ray inelastic, diffraction and imaging studies at synchrotron facilities.

We present a new diamond anvil cell design, hereafter called mBX110, that combines both the advantages of a membrane and screws to generate high pressure. It enables studies at large-scale facilities for many synchrotron X-ray techniques and has the possibility to remotely control the pressure with the membrane as well as the use of the screws in the laboratory. It is fully compatible with various gas-loading systems as well as high/low temperature environments in the lab or at large scale facilities. The mBX110 possesses an opening angle of 85° suitable for single-crystal diffraction or Brillouin spectroscopy and a large side opening of 110° which can be used for X-ray inelastic techniques, such as X-ray Raman scattering spectroscopy, but also for X-ray emission, X-ray fluorescence, or X-ray absorption. An even larger opening of 150° can be manufactured enabling X-ray imaging tomography. We report data obtained with the mBX110 on different beamlines with single-crystal diffraction of stishovite up to 55 GPa, X-ray powder diffraction of rutile-GeO2 and tungsten to 25 GPa and 280 GPa, respectively, X-Ray Raman spectra of the Si L-edge in silica to 95 GPa, and Fe Kß X-ray emission spectra on a basalt glass to 17 GPa.

Resonant inelastic X-ray scattering of magnetic excitations under pressure.

Resonant inelastic X-ray scattering (RIXS) is an extremely valuable tool for the study of elementary, including magnetic, excitations in matter. The latest developments of this technique have mostly been aimed at improving the energy resolution and performing polarization analysis of the scattered radiation, with a great impact on the interpretation and applicability of RIXS. Instead, this article focuses on the sample environment and presents a setup for high-pressure low-temperature RIXS measurements of low-energy excitations. The feasibility of these experiments is proved by probing the magnetic excitations of the bilayer iridate Sr3Ir2O7 at pressures up to 12 GPa.

Sequential Ugi reaction/base-induced ring closing/IAAC protocol toward triazolobenzodiazepine-fused diketopiperazines and hydantoins.

A practical three-step protocol for the assembly of triazolobenzodiazepine-fused diketopiperazines and hydantoins has been developed. The synthesis of these tetracyclic ring systems was initiated by an Ugi reaction, which brought together all necessary functionalities for further transformations. The Ugi adducts were then subjected to a base-induced ring closing and an intramolecular azide-alkyne cycloaddition reaction in succession to obtain highly fused benzodiazepine frameworks.

Stability of iron-bearing carbonates in the deep Earth's interior.

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth's lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. Here we investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mössbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth's geotherm at pressures to ∼50 GPa FeCO3 partially dissociates to form various iron oxides. At higher pressures FeCO3 forms two new structures-tetrairon(III) orthocarbonate Fe43+C3O12, and diiron(II) diiron(III) tetracarbonate Fe22+Fe23+C4O13, both phases containing CO4 tetrahedra. Fe4C4O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth's lower mantle.

The orthorhombic pseudopolymorph of tacrine hydrochloride.

Crystallization of tacrine hydrochloride, an acetylcholinesterase inhibitor used during treatment of mild to moderate Alzheimer's disease, from a water:ethanol solution has resulted in an orthorhombic pseudopolymorph. This orthorhombic form which occurs as a dihydrate shows columns of stacking acridines together with continuous Cl-Owater-Owater-Cl chains and ladder-like ribbons composed of squares and hexagons.

Ligand-controlled product selectivity in palladium-catalyzed domino post-Ugi construction of (spiro)polyheterocycles.

A novel diversity-oriented access to (spiro)polyheterocycles possessing two adjacent quaternary carbon stereocenters is described. By combining an Ugi 4-CR with Pd-catalysis, the possible mode of cyclization is controlled by the appropriate choice of ligands. Using XantPhos, spirooxindoles are selectively generated, while with BINAP fused polycyclic cis-dihydrobenzofurans are obtained with high diastereoselectivity.

Diastereoselective Strategies towards Thia[n]helicenes.

In the present study, we have investigated different strategies for diastereoselective synthesis of thia[n]helicenes. We describe the introduction of different chiral auxiliaries at various positions and investigated their effect in the photocyclization reaction. Different chiral groups were placed at the sterically hindered position of the helical core and their interactions with various solvents and metals like copper were investigated. The use of Cu(I) salts has led to high diastereoselectivity in the photocyclization process and we were successful in obtaining the thia[5]helicene in enantiomerically pure form in good yield. The single diastereomer obtained was characterized by X-ray crystallography. From the study of the barrier of racemization of these thia[5]helicenes, the stability was found to be comparable to unsubstituted tetrathia[7]helicenes and substituted diazadithia[7]helicenes. This approach provides an easy access to enantiopure helicenes.

A versatile and highly efficient post-functionalization method for grafting organic molecules onto Anderson-type polyoxometalates.

A new azide functionalized Anderson polyoxometalate was synthesized, fully characterized and subsequently used as a building block for further POM post-functionalization with organic compounds through a copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Optimization of the reaction conditions led to an efficient, fast, convenient and versatile POM coupling method.

Radical C-H alkylation of BODIPY dyes using potassium trifluoroborates or boronic acids.

A one-step synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono-, di-, tri-, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid-state emissive BODIPY dyes.

Solvent switchable cycloaddition: a (one-pot) metal-free approach towards N-substituted benzo[e]- or [f]isoindolones via C(sp(2))-H functionalization.

The tuning of selective ring closure is a nontrivial challenge in synthetic organic chemistry. Herein we report a solvent switchable metal-free [4 + 2] cycloaddition approach via Csp(2)-H functionalization. The protocol is highly atom economical with water being the only by-product, delivering N-substituted benzo[e]- or [f]isoindolones in high yields.

Enantioselective assembly of a ruthenium(II) polypyridyl complex into a double helix.

Evolution can increase the complexity of matter by self-organization into helical architectures, the best example being the DNA double helix. One common aspect, apparently shared by most of these architectures, is the presence of covalent bonds within the helix backbone. Here, we report the unprecedented crystal structures of a metal complex that self-organizes into a continuous double helical structure, assembled by non-covalent building blocks. Built up solely by weak stacking interactions, this alternating tread stairs-like double helical assembly mimics the DNA double helix structure. Starting from a racemic mixture in aqueous solution, the ruthenium(II) polypyridyl complex forms two polymorphic structures of a left-handed double helical assembly of only the Λ-enantiomer. The stacking of the helices is different in both polymorphs: a crossed woodpile structure versus a parallel columnar stacking.

Homogeneous liquid-liquid extraction of neodymium(III) by choline hexafluoroacetylacetonate in the ionic liquid choline bis(trifluoromethylsulfonyl)imide.

The ionic liquid choline bis(trifluoromethylsulfonyl)imide, [Chol][Tf2N], was used for the extraction of neodymium(III), in combination with choline hexafluoroacetylacetonate, [Chol][hfac], as the extractant. The binary mixture of [Chol][Tf2N] and water shows temperature-dependent phase behavior, with an upper critical solution temperature of 72 °C. A novel extraction technique, homogeneous liquid-liquid extraction (HLLE), was applied to this solvent system. HLLE is based on the use of thermomorphic solvent mixtures and has the advantage of forming a homogeneous phase during mixing. Extraction is not kinetically hindered by an interface and the extraction equilibrium is reached faster than in the case of heterogeneous mixing in conventional solvent extraction. Several extraction parameters were studied for the extraction of neodymium(III) with [Chol][hfac]: temperature, pH, extractant concentration and loading of the ionic liquid phase. A speciation study was performed to determine the stoichiometry of the extracted neodymium(III) complex and a plausible extraction mechanism is proposed. Neodymium is extracted as a tetrakis hexafluoroacetylacetonate complex with one choline cation as counter ion. The crystal structure of the extracted complex showed the presence of a coordination bond between the choline counter ion and the neodymium(III) center, resulting in a coordination number of nine. The stripping of the loaded neodymium and the influence of acid and extractant concentrations on the phase behavior of the [Chol][Tf2N]-H2O system were investigated.

Unexpected regio- and chemoselectivity of cationic gold-catalyzed cycloisomerizations of propargylureas: access to tetrasubstituted 3,4-dihydropyrimidin-2(1H)-ones.

Cationic gold-catalyzed cycloisomerizations of propargylureas, derived in situ from secondary propargylamines and aryl or alkyl isocyanates, have been studied. The reaction outcome was found to be different from what was previously observed for the tosyl isocyanate-derived ureas in terms of both regio- and chemoselectivity. As a result, the current protocol offers efficient access to the 3,4-dihydropyrimidin-2(1H)-one core through the 6-endo-dig N-cyclization.

8-HaloBODIPYs and their 8-(C, N, O, S) substituted analogues: solvent dependent UV-vis spectroscopy, variable temperature NMR, crystal structure determination, and quantum chemical calculations.

The UV-vis electronic absorption and fluorescence emission properties of 8-halogenated (Cl, Br, I) difluoroboron dipyrrin (or 8-haloBODIPY) dyes and their 8-(C, N, O, S) substituted analogues are reported. The nature of the meso-substituent has a significant influence on the spectral band positions, the fluorescence quantum yields, and lifetimes. As a function of the solvent, the spectral maxima of all the investigated dyes are located within a limited wavelength range. The spectra of 8-haloBODIPYs display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. Conversely, fluorophores with 8-phenylamino (7), 8-benzylamino (8), 8-methoxy (9), and 8-phenoxy (10) groups emit in the blue range of the visible spectrum and generally have larger Stokes shifts than common BODIPYs, whereas 8-(2-phenylethynyl)BODIPY (6) has red-shifted spectra compared to ordinary BODIPY dyes. Fluorescence lifetimes for 6, 8, and 10 have been measured for a large set of solvents and the solvent effect on their absorption and emission maxima has been analyzed using the generalized Catalán solvent scales. Restricted rotation about the C8-N bond in 7 and 8 has been observed via temperature dependent (1)H NMR spectroscopy, whereas for 10 the rotation about the C8-O bond is not hindered. The crystal structure of 8 demonstrates that the short C8-N bond has a significant double character and that this N atom exhibits a trigonal planar geometry. The crystal structure of 10 shows a short C8-O bond and an intramolecular C-H···π interaction. Quantum-chemical calculations have been performed to assess the effect of the meso-substituent on the spectroscopic properties.

Synthesis of (spiro)cyclopentapyridinones via C(sp3)-H functionalization: a post-Ugi gold-catalyzed regioselective tandem cyclization.

A gold-catalyzed regioselective tandem cyclization of N-propynylbutynamide via Csp(3)-H functionalization has been described, providing a distinctive methodology for the architecture of cyclopentapyridinones as well as spirocyclopentapyridinones.

Synthesis and structural exploration of disulfide bridged [2(n)] pillararene-like molecules.

Disulfide bridged pillararene-like macrocycles were synthesized starting from 1,4-dialkoxybenzene and sulfur monochloride. The structure was determined using X-ray diffraction analysis.

Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline}palladium(II) acetonitrile monosolvate.

The title imino-phosphine compound, [PdCl2(C26H22NP)]·CH3CN, was prepared by reaction of N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline with dichlorido(cycloocta-1,5-diene)palladium(II) in dry CH2Cl2. The Pd(II) cation is coordinated by the P and N atoms of the bidentate chelating ligand and by two chloride anions, generating a distorted square-planar coordination geometry. There is a detectable trans influence for the chloride ligands. The methyl group present in this structure has an influence on the crystal packing.

Dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-κ2N,N'}palladium(II) acetonitrile monosolvate.

The title complex, [PdCl(2)(C(20)H(20)N(2))]·CH(3)CN, was synthesized by the reaction of 2-[(2,6-diethylphenyl)iminomethyl]quinoline with dichlorido(cycloocta-1,5-diene)palladium(II) in dry CH(2)Cl(2). The Pd(II) ion is coordinated by two N atoms of the bidentate quinoline ligand and by two chloride anions, generating a distorted square-planar coordination geometry around the metal centre. There is a detectable trans influence for the chloride ligands. The crystal packing is characterized by π-π stacking between the quinoline rings. The use of acetonitrile as the crystallization solvent was essential for obtaining good-quality crystals.