Chemical Control of Spin-Orbit Coupling and Charge Transfer in Vacancy-Ordered Ruthenium(IV) Halide Perovskites.
Angew Chem Int Ed Engl
; 60(10): 5184-5188, 2021 Mar 01.
Article
em En
| MEDLINE
| ID: mdl-33247485
ABSTRACT
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 RuIV halides are presented; A2 RuCl6 and A2 RuBr6 , where A is K, NH4 , 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 Jeff =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.
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MEDLINE
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En
Ano de publicação:
2021
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Article