Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?

The conditions for achieving the maximal unquenched orbital angular momentum <i>L</i> = 3 and the highest magnetic anisotropy in mononuclear 3d complexes with axial coordination symmetry are examined in terms of the ligand field theory. It is shown that, apart from the known linear two-c...

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Main Author: Vladimir S. Mironov
Format: Article
Language:English
Published: MDPI AG 2022-11-01
Series:Inorganics
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Online Access:https://www.mdpi.com/2304-6740/10/12/227
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author Vladimir S. Mironov
author_facet Vladimir S. Mironov
author_sort Vladimir S. Mironov
collection DOAJ
description The conditions for achieving the maximal unquenched orbital angular momentum <i>L</i> = 3 and the highest magnetic anisotropy in mononuclear 3d complexes with axial coordination symmetry are examined in terms of the ligand field theory. It is shown that, apart from the known linear two-coordinate 3d<sup>7</sup> complex Co<sup>II</sup>(C(SiMe<sub>2</sub>ONaph)<sub>3</sub>)<sub>2</sub> characterized by record magnetic anisotropy and single-molecule magnet (SMM) performance (with the largest known spin-reversal barrier <i>U</i><sub>eff</sub> = 450 cm<sup>−1</sup>), the maximal orbital angular momentum <i>L</i> = 3 can also be obtained in linear two-coordinate 3d<sup>2</sup> complexes (V<sup>3+</sup>, Cr<sup>4+</sup>) and in trigonal-prismatic 3d<sup>3</sup> (Cr<sup>3+</sup>, Mn<sup>4+</sup>) and 3d<sup>8</sup> (Co<sup>+</sup>, Ni<sup>2+</sup>) complexes. A comparative assessment of the SMM performance of the 3d<sup>2</sup>, 3d<sup>3</sup> and 3d<sup>8</sup> complexes indicates that they are unlikely to compete with the record linear complex Co<sup>II</sup>(C(SiMe<sub>2</sub>ONaph)<sub>3</sub>)<sub>2</sub>, whose magnetic anisotropy is close to the physical limit for a 3d metal.
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spelling doaj.art-c2bd242bbc504b00aa6d8614eda16e782023-11-24T15:38:04ZengMDPI AGInorganics2304-67402022-11-01101222710.3390/inorganics10120227Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?Vladimir S. Mironov0Shubnikov Institute of Crystallography of Federal Scientific Research Centre “Crystallography and Photonics” of Russian Academy of Sciences, Leninskiy Prospekt 59, Moscow 119333, RussiaThe conditions for achieving the maximal unquenched orbital angular momentum <i>L</i> = 3 and the highest magnetic anisotropy in mononuclear 3d complexes with axial coordination symmetry are examined in terms of the ligand field theory. It is shown that, apart from the known linear two-coordinate 3d<sup>7</sup> complex Co<sup>II</sup>(C(SiMe<sub>2</sub>ONaph)<sub>3</sub>)<sub>2</sub> characterized by record magnetic anisotropy and single-molecule magnet (SMM) performance (with the largest known spin-reversal barrier <i>U</i><sub>eff</sub> = 450 cm<sup>−1</sup>), the maximal orbital angular momentum <i>L</i> = 3 can also be obtained in linear two-coordinate 3d<sup>2</sup> complexes (V<sup>3+</sup>, Cr<sup>4+</sup>) and in trigonal-prismatic 3d<sup>3</sup> (Cr<sup>3+</sup>, Mn<sup>4+</sup>) and 3d<sup>8</sup> (Co<sup>+</sup>, Ni<sup>2+</sup>) complexes. A comparative assessment of the SMM performance of the 3d<sup>2</sup>, 3d<sup>3</sup> and 3d<sup>8</sup> complexes indicates that they are unlikely to compete with the record linear complex Co<sup>II</sup>(C(SiMe<sub>2</sub>ONaph)<sub>3</sub>)<sub>2</sub>, whose magnetic anisotropy is close to the physical limit for a 3d metal.https://www.mdpi.com/2304-6740/10/12/227magnetic anisotropysingle-molecule magnetunquenched orbital momentumspin-reversal barriermononuclear 3d complexesspin-orbit coupling
spellingShingle Vladimir S. Mironov
Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
Inorganics
magnetic anisotropy
single-molecule magnet
unquenched orbital momentum
spin-reversal barrier
mononuclear 3d complexes
spin-orbit coupling
title Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
title_full Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
title_fullStr Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
title_full_unstemmed Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
title_short Reaching the Maximal Unquenched Orbital Angular Momentum <i>L</i> = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
title_sort reaching the maximal unquenched orbital angular momentum i l i 3 in mononuclear transition metal complexes where when and how
topic magnetic anisotropy
single-molecule magnet
unquenched orbital momentum
spin-reversal barrier
mononuclear 3d complexes
spin-orbit coupling
url https://www.mdpi.com/2304-6740/10/12/227
work_keys_str_mv AT vladimirsmironov reachingthemaximalunquenchedorbitalangularmomentumili3inmononucleartransitionmetalcomplexeswherewhenandhow