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The synthesis of polynitrogen compounds is of fundamental importance due to their potential as environmentally-friendly high energy density materials. Attesting to the intrinsic difficulties related to their formation, only three polynitrogen ions, bulk stabilized as salts, are known. Here, magnesium and molecular nitrogen are compressed to about 50 GPa and laser-heated, producing two chemically simple salts of polynitrogen anions, MgN 4 and Mg 2 N 4 . Single-crystal X-ray diffraction reveals infinite anionic polythiazyl-like 1D N-N chains in the crystal structure of MgN 4 and cis -tetranitrogen N 4 4− units in the two isosymmetric polymorphs of Mg 2 N 4 . The cis -tetranitrogen units are found to be recoverable at atmospheric pressure. Our results respond to the quest for polynitrogen entities stable at ambient conditions, reveal the potential of employing high pressures in their synthesis and enrich the nitrogen chemistry through the discovery of other nitrogen species, which provides further possibilities to design improved polynitrogen arrangements. Polynitrogen compounds are potentially promising high energy density materials, but are difficult to synthesize due to their instability. Here, the authors observe the formation, under high pressure, of a Mg 2 N 4 magnesium–tetranitrogen salt which remains stable at ambient conditions.

Theoretical modelling predicts very unusual structures and properties of materials at extreme pressure and temperature conditions 1 , 2 . Hitherto, their synthesis and investigation above 200 gigapascals have been hindered both by the technical complexity of ultrahigh-pressure experiments and by the absence of relevant in situ methods of materials analysis. Here we report on a methodology developed to enable experiments at static compression in the terapascal regime with laser heating. We apply this method to realize pressures of about 600 and 900 gigapascals in a laser-heated double-stage diamond anvil cell 3 , producing a rhenium–nitrogen alloy and achieving the synthesis of rhenium nitride Re 7 N 3 —which, as our theoretical analysis shows, is only stable under extreme compression. Full chemical and structural characterization of the materials, realized using synchrotron single-crystal X-ray diffraction on microcrystals in situ, demonstrates the capabilities of the methodology to extend high-pressure crystallography to the terapascal regime. Pressures of up to 900 gigapascals (9 million atmospheres) are achieved in a laser-heated double-stage diamond cell, enabling the synthesis of Re 7 N 3 , and materials characterization is performed in situ using single-crystal X-ray diffraction.

Feldspars are rock-forming minerals that make up most of the Earth’s crust. Along the mantle geotherm, feldspars are stable at pressures up to 3 GPa and may persist metastably at higher pressures under cold conditions. Previous structural studies of feldspars are limited to ~10 GPa, and have shown that the dominant mechanism of pressure-induced deformation is the tilting of AlO 4 and SiO 4 tetrahedra in a tetrahedral framework. Herein, based on results of in situ single-crystal X-ray diffraction studies up to 27 GPa, we report the discovery of new high-pressure polymorphs of the feldspars anorthite (CaSi 2 Al 2 O 8 ), albite (NaAlSi 3 O 8 ) , and microcline (KAlSi 3 O 8 ). The phase transitions are induced by severe tetrahedral distortions, resulting in an increase in the Al and/or Si coordination number. High-pressure phases derived from feldspars could persist at depths corresponding to the Earth upper mantle and could possibly influence the dynamics and fate of cold subducting slabs. Feldspars are stable at pressures up to 3 GPa along the mantle geotherm, but they can persist metastably at higher pressures at colder conditions. Here, above 10 GPa the authors find  new high-pressure polymorphs of feldspars that could persist at depths corresponding to the Earth’s upper mantle, potentially influencing the dynamics and fate of cold subducting slabs.

High-pressure synthesis in diamond anvil cells can yield unique compounds with advanced properties, but often they are either unrecoverable at ambient conditions or produced in quantity insufficient for properties characterization. Here we report the synthesis of metallic, ultraincompressible ( K 0  = 428(10) GPa), and very hard (nanoindentation hardness 36.7(8) GPa) rhenium nitride pernitride Re 2 (N 2 )(N) 2 . Unlike known transition metals pernitrides Re 2 (N 2 )(N) 2 contains both pernitride N 2 4− and discrete N 3− anions, which explains its exceptional properties. Re 2 (N 2 )(N) 2 can be obtained via a reaction between rhenium and nitrogen in a diamond anvil cell at pressures from 40 to 90 GPa and is recoverable at ambient conditions. We develop a route to scale up its synthesis through a reaction between rhenium and ammonium azide, NH 4 N 3 , in a large-volume press at 33 GPa. Although metallic bonding is typically seen incompatible with intrinsic hardness, Re 2 (N 2 )(N) 2 turned to be at a threshold for superhard materials. High pressure experiments may yield materials with unusual combinations of properties, but typically in small amounts and unstable. Here the authors synthesize millimeter-sized samples of metallic, ultraincompressible and very hard rhenium nitride pernitride, recoverable at ambient conditions.

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 FeCO 3 partially dissociates to form various iron oxides. At higher pressures FeCO 3 forms two new structures—tetrairon(III) orthocarbonate Fe 4 3+ C 3 O 12 , and diiron(II) diiron(III) tetracarbonate Fe 2 2+ Fe 2 3+ C 4 O 13 , both phases containing CO 4 tetrahedra. Fe 4 C 4 O 13 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. Carbonates are shown to exist in the lower mantle as seen in diamond inclusions, but thermodynamic constraints are poorly understood. Here, the authors synthesise two new iron carbonate compounds and find that self-oxidation-reduction reactions can preserve carbonates in the mantle.

Metal carbides are known to contain small carbon units similar to those found in the molecules of methane, acetylene, and allene. However, for numerous binary systems ab initio calculations predict the formation of unusual metal carbides with exotic polycarbon units, [C 6 ] rings, and graphitic carbon sheets at high pressure (HP). Here we report the synthesis and structural characterization of a HP-CaC 2 polymorph and a Ca 3 C 7 compound featuring deprotonated polyacene-like and para -poly(indenoindene)-like nanoribbons, respectively. We also demonstrate that carbides with infinite chains of fused [C 6 ] rings can exist even at conditions of deep planetary interiors ( ~ 140 GPa and ~3300 K). Hydrolysis of high-pressure carbides may provide a possible abiotic route to polycyclic aromatic hydrocarbons in Universe. The authors demonstrate that carbides with infinite chains of fused [C6] and [C5] rings are synthesized at deep planetary pressures and temperatures. Hydrolysis of these carbides may lead to polycyclic aromatic hydrocarbons in the Universe.

The oxidation state of iron in Earth’s mantle is well known to depths of approximately 200 km, but has not been characterized in samples from the lowermost upper mantle (200–410 km depth) or the transition zone (410–660 km depth). Natural samples from the deep (>200 km) mantle are extremely rare, and are usually only found as inclusions in diamonds. Here we use synchrotron Mössbauer source spectroscopy complemented by single-crystal X-ray diffraction to measure the oxidation state of Fe in inclusions of ultra-high pressure majoritic garnet in diamond. The garnets show a pronounced increase in oxidation state with depth, with Fe3+/(Fe3++ Fe2+) increasing from 0.08 at approximately 240 km depth to 0.30 at approximately 500 km depth. The latter majorites, which come from pyroxenitic bulk compositions, are twice as rich in Fe3+ as the most oxidized garnets from the shallow mantle. Corresponding oxygen fugacities are above the upper stability limit of Fe metal. This implies that the increase in oxidation state is unconnected to disproportionation of Fe2+ to Fe3+ plus Fe0. Instead, the Fe3+ increase with depth is consistent with the hypothesis that carbonated fluids or melts are the oxidizing agents responsible for the high Fe3+ contents of the inclusions.

Beryllium oxides have been extensively studied due to their unique chemical properties and important technological applications. Typically, in inorganic compounds beryllium is tetrahedrally coordinated by oxygen atoms. Herein based on results of in situ single crystal X-ray diffraction studies and ab initio calculations we report on the high-pressure behavior of CaBe 2 P 2 O 8 , to the best of our knowledge the first compound showing a step-wise transition of Be coordination from tetrahedral (4) to octahedral (6) through trigonal bipyramidal (5). It is remarkable that the same transformation route is observed for phosphorus. Our theoretical analysis suggests that the sequence of structural transitions of CaBe 2 P 2 O 8 is associated with the electronic transformation from predominantly molecular orbitals at low pressure to the state with overlapping electronic clouds of anions orbitals. Beryllium in inorganic compounds is usually coordinated to four oxygen atoms, but higher coordination numbers have been predicted. Here the authors observe a pressure induced stepwise transition in CaBe 2 P 2 O 8 where Be coordination changes to trigonal-bipyramidal and octahedral, implying that d orbitals are not mandatory for high coordination.

Studies of high-entropy materials contribute to various fields of science and reveal ever more exciting properties of applied interest. Here, we perform a study of the resistance of a Cantor alloy (CoCrFeNiMn) to hydrogen through high-pressure experiments at elevated temperatures by X-ray and neutron time-of-flight experiments and ab initio calculations. We report formation of an fcc hydride based on the Cantor alloy composition. We also provide its characterization, including an estimate of hydrogen content. These findings contribute to the growing body of knowledge on the complex chemistry of high-entropy alloys and high-entropy hydrides. This study shows that the Cantor alloy (CoCrFeNiMn), inert to hydrogen at room temperature, forms a stoichiometric hydride under high-pressure, high-temperature conditions, supported by X-ray, neutron diffraction, and ab initio calculations.

The pressure-induced Mott insulator-to-metal transitions are often accompanied by a collapse of magnetic interactions associated with delocalization of 3 d electrons and high-spin to low-spin (HS-LS) state transition. Here, we address a long-standing controversy regarding the high-pressure behavior of an archetypal Mott insulator FeBO 3 and show the insufficiency of a standard theoretical approach assuming a conventional HS-LS transition for the description of the electronic properties of the Mott insulators at high pressures. Using high-resolution x-ray diffraction measurements supplemented by Mössbauer spectroscopy up to pressures ~ 150 GPa, we document an unusual electronic state characterized by a “mixed” HS/LS state with a stable abundance ratio realized in the R 3 ¯ c crystal structure with a single Fe site within a wide pressure range of ~ 50–106 GPa. Our results imply an unconventional cooperative (and probably dynamical) nature of the ordering of the HS/LS Fe sites randomly distributed over the lattice, resulting in frustration of magnetic moments.