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Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes

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Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes. / Thomsen, Maja K.; Nyvang, Andreas; Walsh, James P.S. et al.

In: Inorganic Chemistry, Vol. 58, No. 5, 2019, p. 3211-3218.

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Thomsen MK, Nyvang A, Walsh JPS, Bunting PC, Long JR, Neese F et al. Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes. Inorganic Chemistry. 2019;58(5):3211-3218. doi: 10.1021/acs.inorgchem.8b03301

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@article{dd78e0549dbb4821bb2533f514458500,
title = "Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes",
abstract = " A breakthrough in the study of single-molecule magnets occurred with the discovery of zero-field slow magnetic relaxation and hysteresis for the linear iron(I) complex [Fe(C(SiMe 3 ) 3 ) 2 ] - (1), which has one of the largest spin-reversal barriers among mononuclear transition-metal single-molecule magnets. Theoretical studies have suggested that the magnetic anisotropy in 1 is made possible by pronounced stabilization of the iron dz 2 orbital due to 3dz 2 -4s mixing, an effect which is predicted to be less pronounced in the neutral iron(II) complex Fe(C(SiMe 3 ) 3 ) 2 (2). However, experimental support for this interpretation has remained lacking. Here, we use high-resolution single-crystal X-ray diffraction data to generate multipole models of the electron density in these two complexes, which clearly show that the iron dz 2 orbital is more populated in 1 than in 2. This result can be interpreted as arising from greater stabilization of the dz 2 orbital in 1, thus offering an unprecedented experimental rationale for the origin of magnetic anisotropy in 1. ",
keywords = "ABSENCE, ANISOTROPY, ATOMS, FIELD, HIGH-SPIN, JAHN-TELLER DISTORTION, RELAXATION",
author = "Thomsen, {Maja K.} and Andreas Nyvang and Walsh, {James P.S.} and Bunting, {Philip C.} and Long, {Jeffrey R.} and Frank Neese and Michael Atanasov and Alessandro Genoni and Jacob Overgaard",
year = "2019",
doi = "10.1021/acs.inorgchem.8b03301",
language = "English",
volume = "58",
pages = "3211--3218",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "AMER CHEMICAL SOC",
number = "5",

}

RIS

TY - JOUR

T1 - Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes

AU - Thomsen, Maja K.

AU - Nyvang, Andreas

AU - Walsh, James P.S.

AU - Bunting, Philip C.

AU - Long, Jeffrey R.

AU - Neese, Frank

AU - Atanasov, Michael

AU - Genoni, Alessandro

AU - Overgaard, Jacob

PY - 2019

Y1 - 2019

N2 - A breakthrough in the study of single-molecule magnets occurred with the discovery of zero-field slow magnetic relaxation and hysteresis for the linear iron(I) complex [Fe(C(SiMe 3 ) 3 ) 2 ] - (1), which has one of the largest spin-reversal barriers among mononuclear transition-metal single-molecule magnets. Theoretical studies have suggested that the magnetic anisotropy in 1 is made possible by pronounced stabilization of the iron dz 2 orbital due to 3dz 2 -4s mixing, an effect which is predicted to be less pronounced in the neutral iron(II) complex Fe(C(SiMe 3 ) 3 ) 2 (2). However, experimental support for this interpretation has remained lacking. Here, we use high-resolution single-crystal X-ray diffraction data to generate multipole models of the electron density in these two complexes, which clearly show that the iron dz 2 orbital is more populated in 1 than in 2. This result can be interpreted as arising from greater stabilization of the dz 2 orbital in 1, thus offering an unprecedented experimental rationale for the origin of magnetic anisotropy in 1.

AB - A breakthrough in the study of single-molecule magnets occurred with the discovery of zero-field slow magnetic relaxation and hysteresis for the linear iron(I) complex [Fe(C(SiMe 3 ) 3 ) 2 ] - (1), which has one of the largest spin-reversal barriers among mononuclear transition-metal single-molecule magnets. Theoretical studies have suggested that the magnetic anisotropy in 1 is made possible by pronounced stabilization of the iron dz 2 orbital due to 3dz 2 -4s mixing, an effect which is predicted to be less pronounced in the neutral iron(II) complex Fe(C(SiMe 3 ) 3 ) 2 (2). However, experimental support for this interpretation has remained lacking. Here, we use high-resolution single-crystal X-ray diffraction data to generate multipole models of the electron density in these two complexes, which clearly show that the iron dz 2 orbital is more populated in 1 than in 2. This result can be interpreted as arising from greater stabilization of the dz 2 orbital in 1, thus offering an unprecedented experimental rationale for the origin of magnetic anisotropy in 1.

KW - ABSENCE

KW - ANISOTROPY

KW - ATOMS

KW - FIELD

KW - HIGH-SPIN

KW - JAHN-TELLER DISTORTION

KW - RELAXATION

UR - http://www.scopus.com/inward/record.url?scp=85062103318&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b03301

DO - 10.1021/acs.inorgchem.8b03301

M3 - Journal article

C2 - 30762344

AN - SCOPUS:85062103318

VL - 58

SP - 3211

EP - 3218

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -