Record High Magnetic Anisotropy in Three-Coordinate Mn III and Cr II Complexes: A Theoretical Perspective.

Authors :: Sarkar A
Jose R
Ghosh H
Rajaraman G
Source :: Inorganic chemistry [Inorg Chem] 2021 Jul 05; Vol. 60 (13), pp. 9680-9687. Date of Electronic Publication: 2021 Jun 23.
Publication Year :: 2021
Abstract: Ab initio calculations performed in two three-coordinate complexes [Mn{N(SiMe <subscript>3</subscript> ) <subscript>2</subscript> } <subscript>3</subscript> ] ( 1 ) and [K(18-crown-6) (Et <subscript>2</subscript> O) <subscript>2</subscript> ][Cr{N(SiMe <subscript>3</subscript> ) <subscript>2</subscript> } <subscript>3</subscript> ] ( 2 ) reveal record-high magnetic anisotropy with the D values -64 and -15 cm <superscript>-1</superscript> , respectively, enlisting d <superscript>4</superscript> ions back in the race for single-ion magnets. A detailed spin-vibrational analysis performed of 1 and 2 suggests dominance under barrier relaxation due to the flexible coordination spheres around the metal ion. Furthermore, several in silico models were constructed by varying the nature of donor atoms based on the X-ray structure of 1 and 2 , unveiling much larger anisotropy and robust single-ion magnet (SIM) characteristics for some of the models offering design clues for low-coordinate transition-metal SIMs.

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