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000022478 084__ $$2WoS$$aChemistry, Inorganic & Nuclear
000022478 1001_ $$0P:(DE-HGF)0$$aMalaestean, I.L.$$b0
000022478 245__ $$aMacrocycles based on magnetically functionalized zirconium oxide clusters
000022478 260__ $$aNew York, NY [u.a.]$$bElsevier$$c2012
000022478 300__ $$a72 - 77
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000022478 440_0 $$026383$$aInorganica Chimica Acta$$v380
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000022478 500__ $$aAmes Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract No. DE-AC02-07CH11358.
000022478 520__ $$aIn the presence of 4,4'-bipyridine and Co(II) or Ni(II) groups, which are coordinatively constrained by bis-alkoxyamine chelating groups, dimeric [(Zr6O4)-O-IV(OH)(4)(RCOO)(12)](2) clusters rearrange to {Zr12O11(OH)(11)(RCOO)(16)} frameworks featuring highly condensed zirconium oxide cores. These {Zr-12} groups subsequently each coordinate to three M(II) groups and self-assemble via two bridging 4,4'-bpy into 2.6 nm {M6Zr24}type macrocycles of composition [M6Zr24O22(OH)(22)(C2H5COO)(40)(Hmdea)(2)(H(2)mdea)(4)(4,4'-bpy)(2)]. Surprisingly, two M(II) sites peripherally attached to the {Zr-12} frameworks adopt a rare eightfold coordination mode where the M2+ ions reside in a distorted square antiprismatic O7N environment. Magnetic measurements reveal that the zirconium oxide fragments efficiently mediate antiferromagnetic exchange between Ni2+ spin centers, whereas in case of the virtually isostructural Co2+ derivative pronounced ligand field asymmetry causes single-ion effects to significantly influence the low-field susceptibility data. (C) 2011 Elsevier B. V. All rights reserved.
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000022478 65320 $$2Author$$aHeterometallic complexes
000022478 65320 $$2Author$$aMagnetic properties
000022478 65320 $$2Author$$aZirconium compounds
000022478 65320 $$2Author$$aMacrocycles
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