In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2015, No. 11 ( 2015-04), p. 1872-1901
Abstract:
Under anaerobic conditions, the reactions of cobalt(II) and nickel(II) acetate tetrahydrate with 2,6‐pyridinedimethanol (H 2 L 2 , 3 ) in anhydrous acetonitrile afforded two tetranuclear metal(II) complexes [M II 4 (HL 2 ) 4 (OAc) 4 ] ( 4 ; M II = Co 2+ , Ni 2+ ) with a [M 4 (μ 3 ‐O) 4 ] 4+ cubane core. X‐ray structural analyses revealed that both M II cubanes 4a· 2CH 3 OH and 4b· 2CH 3 OH are isostructural and crystallize in the tetragonal space group I 4 1 / acd with eight molecules in the unit cell. In the solid state, the orientation of the cubane cores of 4 and the formation of a 3D framework were controlled by π–π interactions as well as intra‐ and intermolecular O–H ··· O hydrogen bonds. Variable‐temperature magnetic susceptibility measurements revealed that the cubanes 4 show a ferrimagnetic coupling scheme that leads to a diamagnetic ground state for both complexes. Core‐level X‐ray photoelectron spectroscopy confirmed that the Co and Ni ions in 4a and 4b are in a divalent state. X‐ray magnetic circular dichroism was performed to extract the spin and orbital contributions to the Co and Ni magnetic moments. We compared the experimental results of the local electronic structures around the Co 2+ ions in 4a and the Ni 2+ ions in 4b with charge‐transfer multiplet simulations.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2015.11
DOI:
10.1002/ejic.201402988
Language:
English
Publisher:
Wiley
Publication Date:
2015
detail.hit.zdb_id:
1475009-0
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