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Site preferences in hetero-metallic [Fe9−xNix] clusters: a combined crystallographic, spectroscopic and theoretical analysis

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Abstract

The reaction of mixtures of Fe(O2CMe)2·2H2O and Ni(O2CMe)2·4H2O of various compositions with di-2-pyridyl ketone (py2CO, dpk) in MeCN under an inert atmosphere afforded a family of hetero-metallic enneanuclear clusters with general formula [Fe9−xNix4-OH)2(O2CMe)8(py2CO2)4] (2, x = 1.00; 3: x = 6.02; 4, x = 7.46; 5, x = 7.81). Clusters 2–5 are isomorphous to the homo-metallic [Fe9] cluster (1) previously reported by some of us, and also isostructural to the known homo-metallic [Ni9] cluster. All four clusters contain a central MII ion in an unusual 8-coordinate site and eight peripheral MII ions in distorted octahedral environments. The distribution of FeII and NiII ions over these two distinct coordination sites in 2–5 can be established through a combination of X-ray fluorescence and Mössbauer spectroscopies, which show that FeII preferentially occupies the unique 8-coordinate metal site while NiII accumulates in the octahedral holes. Density functional theory indicates that the distribution of ions across the two sites arises not from any intrinsic preference of the FeII ions for the 8-coordinate sites, but rather because of the large ligand field stabilization energy available to NiII in octahedral coordination.

Graphical abstract: Site preferences in hetero-metallic [Fe9−xNix] clusters: a combined crystallographic, spectroscopic and theoretical analysis

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Publication details

The article was received on 08 Aug 2017, accepted on 11 Sep 2017 and first published on 11 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02930F
Citation: Dalton Trans., 2017, Advance Article
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    Site preferences in hetero-metallic [Fe9−xNix] clusters: a combined crystallographic, spectroscopic and theoretical analysis

    A. N. Georgopoulou, K. Al-Ameed, A. K. Boudalis, D. F. Anagnostopoulos, V. Psycharis, J. E. McGrady, Y. Sanakis and C. P. Raptopoulou, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02930F

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