Spin-Orbit Interactions in Osmium Complexes

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Osmium compounds with the Os5d4 electron configuration and an octahedral environment of neighboring atoms attract much attention due to the influence of the spin-orbit interaction on the appearance of magnetic properties in materials. XANES spectroscopy makes it possible to obtain information about the magnitude of the spin-orbit interaction from measuring the intensity ratio of lines near the absorption edges. The influence of the spin-orbit interaction on the XANES OsL2,3 spectra in osmium compounds having an octahedral halogen environment of osmium atoms has been studied. Two types of systems have been investigated: isolated osmium clusters in complex compounds and OsCl4 compound containing polymeric chains of Os connected by bridging Cl atoms. Magnetic susceptibility measurements show a non-magnetic ground state and Van Vleck paramagnetism in the case of isolated clusters and a non-zero magnetic moment over the entire temperature range in OsCl4. As a result of measurements of the XANES spectra, high values of the line intensity ratio near the OsL3/L2 absorption edges have been obtained, which is associated with a strong influence of the spin-orbit interaction on the electronic structure. Theoretical analysis of the XANES spectra of Os compounds with different ligands and outer-sphere cations shows that the electronic structure and magnetic properties depend on the spin-orbit interaction, the crystal field splitting, the electron pairing energy, and non-cubic distortions of the Os environment.

作者简介

I. Asanov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

编辑信件的主要联系方式.
Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

A. Fedorenko

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

D. Vasilchenko

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

M. Grebenkina

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

A. Lavrov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

I. Korol’kov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

V. Kriventsov

Federal Research Center Boreskov Institute of Catalysis

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

S. Trubina

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

T. Asanova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS

Email: asan@niic.nsc.ru
Russia, 630090, Novosibirsk

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版权所有 © И.П. Асанов, А.Д. Федоренко, Д.Б. Васильченко, М.А. Гребенкина, А.Н. Лавров, И.В. Корольков, В.В. Кривенцов, С.В. Трубина, Т.И. Асанова, 2023

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