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Structural Diversity and Magnetic Properties of Hybrid Ruthenium Halide Perovskites and Related Compounds
Author(s) -
Vishnoi Pratap,
Zuo Julia L.,
Strom T. Amanda,
Wu Guang,
Wilson Stephen D.,
Seshadri Ram,
Cheetham Anthony K.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003095
Subject(s) - crystallography , octahedron , orthorhombic crystal system , ruthenium , perovskite (structure) , halide , space group , chemistry , crystal structure , group (periodic table) , materials science , inorganic chemistry , x ray crystallography , catalysis , biochemistry , physics , organic chemistry , diffraction , optics
There has been a great deal of recent interest in extended compounds containing Ru 3+ and Ru 4+ in light of their range of unusual physical properties. Many of these properties are displayed in compounds with the perovskite and related structures. Here we report an array of structurally diverse hybrid ruthenium halide perovskites and related compounds: MA 2 Ru X 6 ( X =Cl or Br), MA 2 M RuX 6 ( M =Na, K or Ag; X =Cl or Br) and MA 3 Ru 2 X 9 ( X =Br) based upon the use of methylammonium (MA=CH 3 NH 3 + ) on the perovskite A site. The compounds MA 2 Ru X 6 with Ru 4+ crystallize in the trigonal space group R 3 ‾ m and can be described as vacancy‐ordered double‐perovskites. The ordered compounds MA 2 M Ru X 6 with M + and Ru 3+ crystallize in a structure related to BaNiO 3 with alternating MX 6 and Ru X 6 face‐shared octahedra forming linear chains in the trigonal P 3 ‾ m space group. The compound MA 3 Ru 2 Br 9 crystallizes in the orthorhombic Cmcm space group and displays pairs of face‐sharing octahedra forming isolated Ru 2 Br 9 moieties with very short Ru–Ru contacts of 2.789 Å. The structural details, including the role of hydrogen bonding and dimensionality, as well as the optical and magnetic properties of these compounds are described. The magnetic behavior of all three classes of compounds is influenced by spin–orbit coupling and their temperature‐dependent behavior has been compared with the predictions of the appropriate Kotani models.