X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged Dy(III)-Cr(III) cluster obtained by fluoride abstraction from cis-[Cr(III)F2(phen)2](+).
An isostructural series of dinuclear chromium(III)-lanthanide(III) clusters is formed by fluoride abstraction of cis-[CrF2(phen)2](+) by Ln(3+) resulting in LnF3 and methoxide-bridged Cr-Ln clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [Cr(III)(phen)2(μ-MeO)2Ln(NO3)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 mJ = ±13/2, and the first excited doublet is found to be mJ = ±11/2 at an energy of δ = 57(21) cm(-1). The Cr(III) ion exhibits a uniaxial anisotropy of DCr = -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.
Swiss Light Source, Paul Scherrer Institut , CH-5232 Villigen PSI, Switzerland.
Jan
J
Dreiser
Kasper S
KS
Pedersen
Torben
T
Birk
Magnus
M
Schau-Magnussen
Cinthia
C
Piamonteze
Stefano
S
Rusponi
Thomas
T
Weyhermüller
Harald
H
Brune
Frithjof
F
Nolting
Jesper
J
Bendix
D002857:Chromium / Q000737:chemistry*; D002942:Circular Dichroism; D004419:Dysprosium / Q000737:chemistry*; D005459:Fluorides / Q000737:chemistry*; D060526:Magnetic Fields; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014965:X-Rays
D009942:Organometallic Compounds; D002857:Chromium; D004419:Dysprosium; D005459:Fluorides; D000432:Methanol