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Chemical Control of Spin‐Orbit Coupling and Charge Transfer in Vacancy‐Ordered Ruthenium(IV) Halide Perovskites
Author(s) -
Vishnoi Pratap,
Zuo Julia L.,
Cooley Joya A.,
Kautzsch Linus,
GómezTorres Alejandra,
Murillo Jesse,
Fortier Skye,
Wilson Stephen D.,
Seshadri Ram,
Cheetham Anthony K.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013383
Subject(s) - halide , chemistry , delocalized electron , spin–orbit interaction , perovskite (structure) , vacancy defect , charge (physics) , ruthenium , metal , inorganic chemistry , chemical physics , crystallography , condensed matter physics , physics , biochemistry , organic chemistry , quantum mechanics , catalysis
Vacancy‐ordered double perovskites are attracting significant attention due to their chemical diversity and interesting optoelectronic properties. With a view to understanding both the optical and magnetic properties of these compounds, two series of Ru IV halides are presented; A 2 RuCl 6 and A 2 RuBr 6 , where A is K, NH 4 , Rb or Cs. We show that the optical properties and spin‐orbit coupling (SOC) behavior can be tuned through changing the A cation and the halide. Within a series, the energy of the ligand‐to‐metal charge transfer increases as the unit cell expands with the larger A cation, and the band gaps are higher for the respective chlorides than for the bromides. The magnetic moments of the systems are temperature dependent due to a non‐magnetic ground state with J eff =0 caused by SOC. Ru‐ X covalency, and consequently, the delocalization of metal d ‐electrons, result in systematic trends of the SOC constants due to variations in the A cation and the halide anion.