A missing high-spin molecule in the family of cyanido-bridged heptanuclear heterometal complexes, [(LCuII)6FeIII(CN)6]3+, and its CoIII and CrIII analogues, accompanied in the crystal by a novel octameric water cluster

Three isostructural cyanido-bridged heptanuclear complexes, [{CuII(saldmen)(H2O)}6{MIII(CN)6}](ClO4)3[middle dot]8H2O (M = FeIII2; CoIII, 3; CrIII4), have been obtained by reacting the dinuclear copper(ii) complex, [Cu2(saldmen)2([small mu ]-H2O)(H2O)2](ClO4)2[middle dot]2H2O 1, with K3[Co(CN)6], K4...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2010-01, Vol.39 (20), p.4838-4847
Main Authors: Maxim, Catalin, Sorace, Lorenzo, Khuntia, Panchanana, Madalan, Augustin M, Kravtsov, Victor, Lascialfari, Alessandro, Caneschi, Andrea, Journaux, Yves, Andruh, Marius
Format: Article
Language:English
Subjects:
Cations
Clusters
Condensing
Couplings
Crystals
Ferromagnetism
MAGNETIC PROPERTIES
Schiff bases
SPECTRA
WATER
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Summary:Three isostructural cyanido-bridged heptanuclear complexes, [{CuII(saldmen)(H2O)}6{MIII(CN)6}](ClO4)3[middle dot]8H2O (M = FeIII2; CoIII, 3; CrIII4), have been obtained by reacting the dinuclear copper(ii) complex, [Cu2(saldmen)2([small mu ]-H2O)(H2O)2](ClO4)2[middle dot]2H2O 1, with K3[Co(CN)6], K4[Fe(CN)6], and K3[Cr(CN)6], respectively (Hsaldmen is the Schiff base resulting from the condensation of salicylaldehyde with N,N-dimethylethylenediamine). A unique octameric water cluster, with bicyclo[2,2,2]octane-like structure, is sandwiched between the heptanuclear cations in 2, 3 and 4. The cryomagnetic investigations of compounds 2 and 4 reveal ferromagnetic couplings of the central FeIII or CrIII ions with the CuII ions (JCuFe = +0.87 cm-1, JCuCr = +30.4 cm-1). The intramolecular CuCu exchange interaction in 3, across the diamagnetic cobalt(iii) ion, is -0.3 cm-1. The solid-state 1H-NMR spectra of compounds 2 and 3 have been investigated.
ISSN:1477-9226
1477-9234
DOI:10.1039/B924505G