Possible Peierls Distortion Through Re 2 Dimer Formation in the LaNiO 2 ‐Type Nitrides Ln ReN 2 ( Ln = Pr, Nd)

Angewandte Chemie International Edition, vol. 65, pp. e19710

Abstract

Abstract Nitride perovskites are a recently opened class of materials with a limited number of stable compounds. Notably, anion‐vacancy‐ordered materials such as LaNiO 2 ‐type nitrides are rare despite useful properties such as superconductivity reported for analogous oxides. Here, we report the preparation of two Ln ReN 2 ( Ln = Pr, Nd) materials with a distorted LaNiO 2 ‐type structure at high‐pressure, high‐temperature conditions of a large volume press. Powder X‐ray and neutron diffraction show that the orthorhombic distortion (o‐ Ln ReN 2 ) of the LaNiO 2 ‐aristotype structure is caused by buckling of the ReN 4/2 layers through Re dimerization. Electronic structure analysis reveals that the o‐ Ln ReN 2 materials are composed of classic nitridometallate anions and a cationic intermetallic framework. Moreover, the calculations reveal the driving force of the Re dimerization likely to be from an electronic instability related to a Peierls‐type distortion. We further characterize the magnetic ground state of both materials with magnetization measurements as well as magnetic neutron scattering uncovering a long‐range antiferromagnetic order of Nd 3+ moments in NdReN 2 at T N = 15.5 K. The stability of the compounds is investigated by temperature‐dependent powder X‐ray diffraction showing decomposition of NdReN 2 at ca. 750 °C. The o‐ Ln ReN 2 materials represent a curious class of nitrides at the border of classic nitridometallates, intermetallics, and low‐dimensional complex chemistry.

Authors 7

1. Dominik Werhahn

   Ludwig-Maximilians-Universität München

   Affiliation as printed

   Department Chemistry LMU Munich Butenandtstr. 5–13 81377 Munich Germany

2. Amalina T. Buda

   Ludwig-Maximilians-Universität München

   Affiliation as printed

   Department Chemistry LMU Munich Butenandtstr. 5–13 81377 Munich Germany

3. Simon J. Steinberg Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

4. Pascal Manuel

   Rutherford Appleton Laboratory · ISIS Neutron and Muon Source

   Affiliation as printed

   ISIS Neutron and Muon Source STFC Rutherford Appleton Laboratory Didcot UK

5. C. Ritter

   Institut Laue-Langevin

   Affiliation as printed

   Institut Laue‐Langevin 71 avenue des Martyrs, CS 20156, 38042 Grenoble Cedex 9 France

6. John Paul Attfield

   University of Edinburgh

   Affiliation as printed

   Centre for Science at Extreme Conditions University of Edinburgh Peter Guthrie Tait Road, EH9 3FD Edinburgh UK

7. Simon D. Kloß corresponding

   Ludwig-Maximilians-Universität München

   Affiliation as printed

   Department Chemistry LMU Munich Butenandtstr. 5–13 81377 Munich Germany