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Two Distinct Cu(II)-V(IV) Superexchange Interactions with Similar Bond Angles in a Triangular ?CuV2? Fragment

Journal Article · · Inorganic Chemistry
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The strength and sign of superexchange interactions are often predicted on the basis of the bond angles between magnetic ions, but complications may arise in situations with a nontrivial arrangement of the magnetic orbitals. We report on a novel molecular tetramer compound [Cu(H2O)dmbpy]2[V2O2F8] (dmbpy = 4,4 '-dimethyl-2,2 ' bipyridyl) that is composed of triangular "CuV2" fragments and displays a spin gap behavior. By combining first-principles calculations and electronic models, we reveal that superexchange Cu-V interactions carry drastically diHerent coupling strengths along two Cu-F-V pathways with comparable bond angles in the triangular "CuV2" fragment. Counterintuitively, their strong disparity is found to originate from the restricted symmetry of the half-filled Cu dx2-y2 orbital stabilized by the crystal field, leading to one dominating antiferromagnetic Cu-V coupling in each fragment. We revisit the magnetic properties of the reported spin-gapped chain compound [enH2]Cu(H2O)2[V2O2F8] (enH2 = ethylene diammonium) containing similar triangular "CuV2" fragments, and the magnetic behavior of the molecular tetramer and the chain compounds is rationalized as that of weakly coupled spin dimers and spin trimers, respectively. This work demonstrates that fundamentally diHerent magnetic couplings can be observed between magnetic ions with similar bond angles in a single spin motif, thus providing a strategy to introduce various exchange interactions combined with low dimensionality in heterometallic Cu(II)-V(IV) compounds.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division; Japan Society for the Promotion of Science (JSPS); National Science Foundation (NSF); State of Illinois; Northwestern University - International Institute for Nanotechnology (IIN)
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1989120
Journal Information:
Inorganic Chemistry, Vol. 61, Issue 26
Country of Publication:
United States
Language:
English

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