Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

Thorbjørn Juul Morsing; Stephan P. A. Sauer; Høgni Weihe; Jesper Bendix; Anders Rørbæk Døssing

doi:10.1016/j.ica.2012.10.004

Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

Thorbjørn Juul Morsing, Stephan P. A. Sauer, Høgni Weihe, Jesper Bendix, Anders Rørbæk Døssing

Kemisk Institut

9 Citationer (Scopus)

Abstract

The magnetic susceptibility of the dinuclear chromium(III) complex
[(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-bridged dinuclear Cr(III) system. The applicability of DFT for computational prediction of exchange in strongly coupled chromium(III) dimers was examined and an optimal and accurate modeling approach was devised. By such modeling it was shown possible to reproduce experimental exchange coupling constants with small relative errors typically of less than 10
% ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized.

Originalsprog	Engelsk
Tidsskrift	Inorganica Chimica Acta
Vol/bind	396
Sider (fra-til)	72-77
Antal sider	6
ISSN	0020-1693
DOI	https://doi.org/10.1016/j.ica.2012.10.004
Status	Udgivet - 24 feb. 2013

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10.1016/j.ica.2012.10.004

Citationsformater

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title = "Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands",

abstract = "The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-bridged dinuclear Cr(III) system. The applicability of DFT for computational prediction of exchange in strongly coupled chromium(III) dimers was examined and an optimal and accurate modeling approach was devised. By such modeling it was shown possible to reproduce experimental exchange coupling constants with small relative errors typically of less than 10% ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized.",

author = "Morsing, {Thorbj{\o}rn Juul} and Sauer, {Stephan P. A.} and H{\o}gni Weihe and Jesper Bendix and D{\o}ssing, {Anders R{\o}rb{\ae}k}",

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T1 - Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

AU - Morsing, Thorbjørn Juul

AU - Sauer, Stephan P. A.

AU - Weihe, Høgni

AU - Bendix, Jesper

AU - Døssing, Anders Rørbæk

PY - 2013/2/24

Y1 - 2013/2/24

N2 - The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-bridged dinuclear Cr(III) system. The applicability of DFT for computational prediction of exchange in strongly coupled chromium(III) dimers was examined and an optimal and accurate modeling approach was devised. By such modeling it was shown possible to reproduce experimental exchange coupling constants with small relative errors typically of less than 10% ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized.

AB - The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-bridged dinuclear Cr(III) system. The applicability of DFT for computational prediction of exchange in strongly coupled chromium(III) dimers was examined and an optimal and accurate modeling approach was devised. By such modeling it was shown possible to reproduce experimental exchange coupling constants with small relative errors typically of less than 10% ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized.

U2 - 10.1016/j.ica.2012.10.004

DO - 10.1016/j.ica.2012.10.004

M3 - Journal article

SN - 0020-1693

VL - 396

SP - 72

EP - 77

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

Abstract

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