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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]+
journal contribution
posted on 2012-08-02, 00:00 authored by Jan Dreiser, Kasper S. Pedersen, Torben Birk, Magnus Schau-Magnussen, Cinthia Piamonteze, Stefano Rusponi, Thomas Weyhermüller, Harald Brune, Frithjof Nolting, Jesper BendixAn isostructural series of dinuclear chromium(III)–lanthanide(III)
clusters is formed by fluoride abstraction of cis-[CrF2(phen)2]+ by Ln3+ resulting in LnF3 and methoxide-bridged Cr–Ln
clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [CrIII(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 CrIII–DyIII coupling of j = −0.04(3) cm–1. The DyIII 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 CrIII 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.