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Influence of Molecular and Electronic Structure of Ln3+ Complexes on the Occurrence of Monoionic Magnetism: a Review

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Theoretical and Experimental Chemistry Aims and scope

A Correction to this article was published on 01 November 2022

This article has been updated

The phenomenon of single ion magnetism in Ln3+ coordination compounds and the principles of their rational design are considered. The influence of electronic and chemical structure, as well as the symmetry of the coordination sphere on the value of the energy barrier of magnetic anisotropy, is highlighted. Based on the analysis of the available data in the literature, it is concluded that further efforts in the design of single ion magnets should focus on the development of coordination compounds Dy3 + and Tb3 + with high axiality, in which the strength of the bond between central metal ion and ligands in the apical position far exceeds the appropriate values for ligands in the equatorial plane.

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Abbreviations

c.n.:

coordination number

SA:

square antiprism

CF:

crystal field

MIM:

monoionic magnet

MMM:

monomolecular magnet

SOC:

spin-orbit coupling

∆T :

“tunneling splitting”

TAQT:

thermally activated quantum tunneling

m S :

magnetic quantum number

D :

magnetic anisotropy

U eff :

magnetic anisotropy barrier

τ:

relaxation time

T B :

blocking temperature

J :

total angular momentum

S :

total spin of a molecule in the ground state

J :

exchange interaction parameter, exchange integral

C:

center of cyclopentadienyl(–) or cyclooctatetraenyl (2–) ring

THF:

tetrahydrofuran

DME:

dimethoxyethane

DMF:

dimethylformamide

HMB:

hexamethylbenzene

di:

dioxane

py:

pyridine

4-Mepy:

4-methylpyridine

Ph:

phenyl

iPr:

isopropyl

Cyclh:

cyclohexyl

HMB:

hexamethylbenzene

phen:

phenanthroline

bipy:

2,2 -bipyridine

TfO– :

triflate anion

Tp– :

tris-(3,5-dimethyl-1-pyrazolyl)borate anion

dedtc:

diethyldithiocarbamate

Htbp:

2,4,6-tris-t-butylphenol

TBA+ :

tetrabutylammonium cation

TMA+ :

tetramethylammonium cation

DBC:

2,6-di-tert-butyl-p-cresolate (–)

Btmsm:

bis(trimethylsilyl)methyl (–)

tppo:

triphenylphosphine oxide

DMPE:

1,2-bis(dimethylphosphino)ethane

Dsp– :

3,4-dimethyl-2,5-bis(trimethylsilyl)phosphoryl

H2bbpen:

N,N′-bis(2-hydroxybenzyl)-N,N′-bis(2-picolyl)ethylenediamine

18C6:

18-crown-6

Pc:

phthalocyanine

Cp– :

cyclopentadiene anion

Cpttt – :

1,2,4-tri(tert-butyl)cyclopentadiene anion

Cnt:

cyclononatetraene anion

COT2– :

cyclooctatetraene dianion

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This work was supported by the National Research Fund of Ukraine, grant No. 2020.02/0202.

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  1. L. V. Pysarzhevsky Institute of Physical Chemistry, NAS of Ukraine, Kyiv, Ukraine

    A. V. Pavlishchuk & V. V. Pavlishchuk

  2. Taras Shevchenko Kyiv National University, Kyiv, Ukraine

    A. V. Pavlishchuk

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  1. A. V. Pavlishchuk
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  2. V. V. Pavlishchuk
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Correspondence to A. V. Pavlishchuk.

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Translated from Teoretychna ta Eksperymentalna Khimiya, Vol. 57, No. 3, pp. 135-158, May-June, 2021.

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Pavlishchuk, A.V., Pavlishchuk, V.V. Influence of Molecular and Electronic Structure of Ln3+ Complexes on the Occurrence of Monoionic Magnetism: a Review. Theor Exp Chem 57, 163–190 (2021). https://doi.org/10.1007/s11237-021-09686-2

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  • DOI: https://doi.org/10.1007/s11237-021-09686-2

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