Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative

Chun Y. Chow; Hélène Bolvin; Victoria E. Campbell; Régis Guillot; Jeff W. Kampf; Wolfgang Wernsdorfer; Frédéric Gendron; Jochen Autschbach; Vincent L. Pecoraro; Talal Mallah

doi:10.1039/c5sc01029b

Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy₂ derivative

Chun Y. Chow
, Hélène Bolvin
, Victoria E. Campbell
, Régis Guillot
, Jeff W. Kampf
, Wolfgang Wernsdorfer
, Frédéric Gendron
, Jochen Autschbach
, Vincent L. Pecoraro
, Talal Mallah

Chemistry

University of Michigan, Ann Arbor
Université Toulouse III - Paul Sabatier
Institut de Chimie Moléculaire et des Matériaux d'Orsay
CNRS
SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

130 Scopus citations

Abstract

We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga₄Ln₂(shi^3-)₄(Hshi^2-)₂(H₂shi^-)₂(C₅H₅N)₄(CH₃OH)_x(H₂O)_x]·xC₅H₅N·xCH₃OH·xH₂O (where H₃shi = salicylhydroxamic acid and Ln = Gd^III1; Tb^III2; Dy^III3; Er^III4; Y^III5; Y^III_0.9Dy^III_0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled Dy^III ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy₂ than for the Er₂ complex.

Original language	English
Pages (from-to)	4148-4159
Number of pages	12
Journal	Chemical Science
Volume	6
Issue number	7
DOIs	https://doi.org/10.1039/c5sc01029b
State	Published - Jul 1 2015

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Chow, C. Y., Bolvin, H., Campbell, V. E., Guillot, R., Kampf, J. W., Wernsdorfer, W., Gendron, F., Autschbach, J., Pecoraro, V. L., & Mallah, T. (2015). Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy₂ derivative. Chemical Science, 6(7), 4148-4159. https://doi.org/10.1039/c5sc01029b

@article{9077f8a988bd46d7b315810c46bfa1d2,

title = "Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative",

abstract = "We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3-)4(Hshi2-)2(H2shi-)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex.",

author = "Chow, \{Chun Y.\} and H{\'e}l{\`e}ne Bolvin and Campbell, \{Victoria E.\} and R{\'e}gis Guillot and Kampf, \{Jeff W.\} and Wolfgang Wernsdorfer and Fr{\'e}d{\'e}ric Gendron and Jochen Autschbach and Pecoraro, \{Vincent L.\} and Talal Mallah",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2015.",

year = "2015",

month = jul,

day = "1",

doi = "10.1039/c5sc01029b",

language = "English",

volume = "6",

pages = "4148--4159",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

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}

Chow, CY, Bolvin, H, Campbell, VE, Guillot, R, Kampf, JW, Wernsdorfer, W, Gendron, F, Autschbach, J, Pecoraro, VL & Mallah, T 2015, 'Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy₂ derivative', Chemical Science, vol. 6, no. 7, pp. 4148-4159. https://doi.org/10.1039/c5sc01029b

TY - JOUR

T1 - Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative

AU - Chow, Chun Y.

AU - Bolvin, Hélène

AU - Campbell, Victoria E.

AU - Guillot, Régis

AU - Kampf, Jeff W.

AU - Wernsdorfer, Wolfgang

AU - Gendron, Frédéric

AU - Autschbach, Jochen

AU - Pecoraro, Vincent L.

AU - Mallah, Talal

PY - 2015/7/1

Y1 - 2015/7/1

N2 - We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3-)4(Hshi2-)2(H2shi-)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex.

AB - We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3-)4(Hshi2-)2(H2shi-)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex.

UR - https://www.scopus.com/pages/publications/84935893174

U2 - 10.1039/c5sc01029b

DO - 10.1039/c5sc01029b

M3 - Article

AN - SCOPUS:84935893174

SN - 2041-6520

VL - 6

SP - 4148

EP - 4159

JO - Chemical Science

JF - Chemical Science

IS - 7

ER -

Assessing the exchange coupling in binuclear lanthanide(III) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy₂ derivative

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