Unraveling the Exotic Chemistry of High-Pressure Nitrogen Compounds

• Applicant: Professorin Dr. Natalia Dubrovinskaia, since 2/2022
• Subject Area: Solid State and Surface Chemistry, Material Synthesis ; Inorganic Molecular Chemistry - Synthesis and Characterisation ; Experimental Condensed Matter Physics
• Term: from 2021 to 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 456543021

• Final Report Year: 2025

Final Report Abstract

Nitrogen compounds are among the most fascinating solid-state systems in contemporary materials research and exhibit a captivating variety of electronic and mechanical properties. Monoatomic nitrogen compounds reveal one of the highest known energy densities and extremely strong N–N bonding forces. Despite their excellent suitability as advanced technological materials, nitrogen compounds remain relatively exotic and account for only 4% of all known solids in the ICSD database. The production of these compounds via standardized synthesis methods is largely not possible due to the high stability of the covalent bond in N₂ molecules. However, the development of novel synthesis methods has led to the discovery of many new nitrogen-based solids. These advancements are attributed to innovative highpressure synthesis techniques, which make it possible to discover new chemical processes and physical phenomena. Through high-pressure investigations of nitrogen-containing compounds with (alkali) earth and transition metals, it has been possible to synthesize a first generation of novel nitrogen compounds. The formation of anionic nitrogen dimers ([N₂]ˣ⁻), polydiazenediyls ([N₄]²⁻), cis-tetranitrogens ([N₄]⁴⁻), and pentazolates ([N₅]⁻) under high pressure illustrates the diversity of nitrogen-based chemical high-pressure compounds. Even more remarkable is the fact that, with the exception of polydiazenediyls, all poly-nitrogens remain stable under ambient conditions after being synthesized at high pressures and temperatures, which further enhances the technological potential of these compounds. The aim of this research project was to investigate the high-pressure behavior of nitrogen in combination with selected elements, to synthesize new materials that had not yet been observed under high pressures, and to study their chemical and physical properties.

Publications

• High-Pressure Synthesis of Dirac Materials: Layered van der Waals Bonded BeN₄ Polymorph. Physical Review Letters, 126(17).
  Bykov, Maxim; Fedotenko, Timofey; Chariton, Stella; Laniel, Dominique; Glazyrin, Konstantin; Hanfland, Michael; Smith, Jesse S.; Prakapenka, Vitali B.; Mahmood, Mohammad F.; Goncharov, Alexander F.; Ponomareva, Alena V.; Tasnádi, Ferenc; Abrikosov, Alexei I.; Bin Masood, Talha; Hotz, Ingrid; Rudenko, Alexander N.; Katsnelson, Mikhail I.; Dubrovinskaia, Natalia; Dubrovinsky, Leonid & Abrikosov, Igor A.
  
• High-Pressure Synthesis of the β-Zn3N2 Nitride and the α-ZnN4 and β-ZnN4 Polynitrogen Compounds. Inorganic Chemistry, 60(19), 14594-14601.
  Laniel, Dominique; Aslandukova, Alena A.; Aslandukov, Andrey N.; Fedotenko, Timofey; Chariton, Stella; Glazyrin, Konstantin; Prakapenka, Vitali B.; Dubrovinsky, Leonid S. & Dubrovinskaia, Natalia
  
• High-Pressure Yttrium Nitride, Y5N14, Featuring Three Distinct Types of Nitrogen Dimers. The Journal of Physical Chemistry C, 125(32), 18077-18084.
  Aslandukov, Andrey; Aslandukova, Alena; Laniel, Dominique; Koemets, Iuliia; Fedotenko, Timofey; Yuan, Liang; Steinle-Neumann, Gerd; Glazyrin, Konstantin; Hanfland, Michael; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Anionic N18 Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN6 and Y2N11 at 100 GPa. Angewandte Chemie International Edition, 61(34).
  Aslandukov, Andrey; Trybel, Florian; Aslandukova, Alena; Laniel, Dominique; Fedotenko, Timofey; Khandarkhaeva, Saiana; Aprilis, Georgios; Giacobbe, Carlotta; Lawrence Bright, Eleanor; Abrikosov, Igor A.; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Domain Auto Finder (DAFi) program: the analysis of single-crystal X-ray diffraction data from polycrystalline samples. Journal of Applied Crystallography, 55(5), 1383-1391.
  Aslandukov, Andrey; Aslandukov, Matvii; Dubrovinskaia, Natalia & Dubrovinsky, Leonid
  
• High-pressure Na₃(N₂)₄, Ca₃(N₂)₄, Sr₃(N₂)₄, and Ba(N₂)₃ featuring nitrogen dimers with noninteger charges and anion-driven metallicity. Physical Review Materials, 6(2).
  Laniel, Dominique; Winkler, Bjoern; Fedotenko, Timofey; Aslandukova, Alena; Aslandukov, Andrey; Vogel, Sebastian; Meier, Thomas; Bykov, Maxim; Chariton, Stella; Glazyrin, Konstantin; Milman, Victor; Prakapenka, Vitali; Schnick, Wolfgang; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′‐P3N5, δ‐P3N5 and PN2. Chemistry – A European Journal, 28(62).
  Laniel, Dominique; Trybel, Florian; Néri, Adrien; Yin, Yuqing; Aslandukov, Andrey; Fedotenko, Timofey; Khandarkhaeva, Saiana; Tasnádi, Ferenc; Chariton, Stella; Giacobbe, Carlotta; Bright, Eleanor Lawrence; Hanfland, Michael; Prakapenka, Vitali; Schnick, Wolfgang; Abrikosov, Igor A.; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Aromatic hexazine [N6]4− anion featured in the complex structure of the high-pressure potassium nitrogen compound K9N56. Nature Chemistry, 15(5), 641-646.
  Laniel, Dominique; Trybel, Florian; Yin, Yuqing; Fedotenko, Timofey; Khandarkhaeva, Saiana; Aslandukov, Andrey; Aprilis, Georgios; Abrikosov, Alexei I.; Bin Masood, Talha; Giacobbe, Carlotta; Bright, Eleanor Lawrence; Glazyrin, Konstantin; Hanfland, Michael; Wright, Jonathan; Hotz, Ingrid; Abrikosov, Igor A.; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Stabilization Of The CN35− Anion In Recoverable High‐pressure Ln3O2(CN3) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates. Angewandte Chemie International Edition, 62(47).
  Aslandukov, Andrey; Jurzick, Pascal L.; Bykov, Maxim; Aslandukova, Alena; Chanyshev, Artem; Laniel, Dominique; Yin, Yuqing; Akbar, Fariia I.; Khandarkhaeva, Saiana; Fedotenko, Timofey; Glazyrin, Konstantin; Chariton, Stella; Prakapenka, Vitali; Wilhelm, Fabrice; Rogalev, Andrei; Comboni, Davide; Hanfland, Michael; Dubrovinskaia, Natalia & Dubrovinsky, Leonid
  
• Structure determination of ζ-N2 from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen. Nature Communications, 14(1).
  Laniel, Dominique; Trybel, Florian; Aslandukov, Andrey; Spender, James; Ranieri, Umbertoluca; Fedotenko, Timofey; Glazyrin, Konstantin; Bright, Eleanor Lawrence; Chariton, Stella; Prakapenka, Vitali B.; Abrikosov, Igor A.; Dubrovinsky, Leonid & Dubrovinskaia, Natalia
  
• Synthesis of Ultra‐Incompressible and Recoverable Carbon Nitrides Featuring CN4 Tetrahedra. Advanced Materials, 36(3).
  Laniel, Dominique; Trybel, Florian; Aslandukov, Andrey; Khandarkhaeva, Saiana; Fedotenko, Timofey; Yin, Yuqing; Miyajima, Nobuyoshi; Tasnádi, Ferenc; Ponomareva, Alena V.; Jena, Nityasagar; Akbar, Fariia Iasmin; Winkler, Bjoern; Néri, Adrien; Chariton, Stella; Prakapenka, Vitali; Milman, Victor; Schnick, Wolfgang; Rudenko, Alexander N.; Katsnelson, Mikhail I. ... & Dubrovinskaia, Natalia
  
• Diverse high-pressure chemistry in Y-NH 3 BH 3 and Y–paraffin oil systems. Science Advances, 10(11).
  Aslandukova, Alena; Aslandukov, Andrey; Laniel, Dominique; Yin, Yuqing; Akbar, Fariia Iasmin; Bykov, Maxim; Fedotenko, Timofey; Glazyrin, Konstantin; Pakhomova, Anna; Garbarino, Gaston; Bright, Eleanor Lawrence; Wright, Jonathan; Hanfland, Michael; Chariton, Stella; Prakapenka, Vitali; Dubrovinskaia, Natalia & Dubrovinsky, Leonid
  
• Stabilization of N6 and N8 anionic units and 2D polynitrogen layers in high-pressure scandium polynitrides. Nature Communications, 15(1).
  Aslandukov, Andrey; Aslandukova, Alena; Laniel, Dominique; Khandarkhaeva, Saiana; Yin, Yuqing; Akbar, Fariia I.; Chariton, Stella; Prakapenka, Vitali; Bright, Eleanor Lawrence; Giacobbe, Carlotta; Wright, Jonathan; Comboni, Davide; Hanfland, Michael; Dubrovinskaia, Natalia & Dubrovinsky, Leonid
  
• Synthesis of LaCN3, TbCN3, CeCN5, and TbCN5 Polycarbonitrides at Megabar Pressures. Journal of the American Chemical Society, 146(26), 18161-18171.
  Aslandukov, Andrey; Liang, Akun; Ehn, Amanda; Trybel, Florian; Yin, Yuqing; Aslandukova, Alena; Akbar, Fariia I.; Ranieri, Umbertoluca; Spender, James; Howie, Ross T.; Bright, Eleanor Lawrence; Wright, Jonathan; Hanfland, Michael; Garbarino, Gaston; Mezouar, Mohamed; Fedotenko, Timofey; Abrikosov, Igor A.; Dubrovinskaia, Natalia; Dubrovinsky, Leonid & Laniel, Dominique