X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged DyIII-CrIII cluster obtained by fluoride abstraction from cis-[CrIIIF2(phen)2]+
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X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged DyIII-CrIII cluster obtained by fluoride abstraction from cis-[CrIIIF2(phen)2]+. / Dreiser, Jan; Pedersen, Kasper Steen; Birk, Torben; Schau-Magnussen, Magnus; Piamonteze, Cinthia; Rusponi, Stefano; Weyhermüller, Thomas; Brune, Harald; Nolting, Frithjof; Bendix, Jesper.
I: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Bind 116, Nr. 30, 2012, s. 7842–7847.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged DyIII-CrIII cluster obtained by fluoride abstraction from cis-[CrIIIF2(phen)2]+
AU - Dreiser, Jan
AU - Pedersen, Kasper Steen
AU - Birk, Torben
AU - Schau-Magnussen, Magnus
AU - Piamonteze, Cinthia
AU - Rusponi, Stefano
AU - Weyhermüller, Thomas
AU - Brune, Harald
AU - Nolting, Frithjof
AU - Bendix, Jesper
PY - 2012
Y1 - 2012
N2 - An isostructural series of dinuclear chromium(III)-lanthanide(III) clusters is formed by fluoride abstraction of cis-[CrF(2)(phen)(2)](+) by Ln(3+) resulting in LnF(3) and methoxide-bridged Cr-Ln clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [Cr(III)(phen)(2)(µ-MeO)(2)Ln(NO(3))(4)]·xMeOH (x = 2-2.73). In contrast to fluoride, methoxide bridges in a nonlinear fashion, which facilitates chelation. For 3, X-ray magnetic circular dichroism (XMCD) provides element-specific magnetization curves that are compared to cluster magnetization and susceptibility data acquired by SQUID magnetometry. The combination of XMCD and SQUID is able to resolve very small magnetic coupling values and reveals a weak Cr(III)-Dy(III) coupling of j = -0.04(3) cm(-1). The Dy(III) ion has a ground-state Kramers doublet of m(J) = ±13/2, and the first excited doublet is found to be m(J) = ±11/2 at an energy of d = 57(21) cm(-1). The Cr(III) ion exhibits a uniaxial anisotropy of D(Cr) = -1.7(1.0) cm(-1). Further, we observe that a weak anisotropic coupling of dipolar origin is sufficient to model the data, suggesting that methoxide bridges do not play a significant role in the magnetic coupling for the present systems.
AB - An isostructural series of dinuclear chromium(III)-lanthanide(III) clusters is formed by fluoride abstraction of cis-[CrF(2)(phen)(2)](+) by Ln(3+) resulting in LnF(3) and methoxide-bridged Cr-Ln clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [Cr(III)(phen)(2)(µ-MeO)(2)Ln(NO(3))(4)]·xMeOH (x = 2-2.73). In contrast to fluoride, methoxide bridges in a nonlinear fashion, which facilitates chelation. For 3, X-ray magnetic circular dichroism (XMCD) provides element-specific magnetization curves that are compared to cluster magnetization and susceptibility data acquired by SQUID magnetometry. The combination of XMCD and SQUID is able to resolve very small magnetic coupling values and reveals a weak Cr(III)-Dy(III) coupling of j = -0.04(3) cm(-1). The Dy(III) ion has a ground-state Kramers doublet of m(J) = ±13/2, and the first excited doublet is found to be m(J) = ±11/2 at an energy of d = 57(21) cm(-1). The Cr(III) ion exhibits a uniaxial anisotropy of D(Cr) = -1.7(1.0) cm(-1). Further, we observe that a weak anisotropic coupling of dipolar origin is sufficient to model the data, suggesting that methoxide bridges do not play a significant role in the magnetic coupling for the present systems.
U2 - 10.1021/jp303512a
DO - 10.1021/jp303512a
M3 - Journal article
C2 - 22788870
VL - 116
SP - 7842
EP - 7847
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 30
ER -
ID: 41963495