Publication Type Journal Article
Title Details make the difference: a family of tetranuclear (CuMnIII)-Mn-II complexes with cube-like and double open cube-like cores
Authors Oleh Stetsiuk Oksana V. Nesterova Vladimir N. Kokozay Kostiantyn V. Domasevitch Iryna V. Omelchenko Oleg V. Shishkin Beata Vranovicova Roman Boca Armando J.L. Pombeiro Svitlana R. Petrusenko
Groups CCC
Journal DALTON TRANSACTIONS
Year 2017
Month June
Volume 46
Number 23
Pages 7480-7494
Abstract The direct synthesis approach, namely one-pot reaction of metal powders and ammonium salt with a methanol solution of a polydentate Schiff base (H2L) formed in situ from salicylaldehyde and ethanolamine, has been successfully used for the preparation of the new heterometallic compounds [Cu3Mn (L)(4)(CH3OH)3](I)3 (1), [Cu3Mn(L)(4)(CH3OH)(3)(H2O)] NCS center dot H2O (2), [Cu3Mn(L)(4)(CH3OH)(H2O)(2.55)] Br center dot 0.45H(2)O (3) and [Cu3Mn(L)(4)(H2O)(3.4)]BF4 center dot 0.6H(2)O (4). Crystallographic analysis revealed that 1-4 are based on the tetranuclear core \Cu-3(II) Mn-III(mu 3-O)(4)\ where the metal centres are joined by the oxygen bridges of Schiff base ligands forming a cube-like arrangement. The novel heterometallic compound [Cu3Mn(L)(4)(CH3OH)(3)](2) [Mn(NCS)(4)]center dot 2CH(3)OH (5) has been obtained by the building block approach using the reaction of [Cu(HL)(2)] with manganese acetate and NH4NCS in methanol. The crystal structure of 5 revealed the \Cu-3(II) Mn-III(mu-O) (2)(mu(3)-O)(2)\ metal core which can be viewed as a double open cube. In spite of a similar \Cu3MnO4\ atom set in the cores of 1-5, the complexes show rather different molecular structures and significantly differ by the number and combinations of coordinated CH3OH/H2O solvent molecules. Variable-temperature (2-300 K) magnetic susceptibility along with variable-field magnetization measurements of 1-5 showed a decrease of the effective magnetic moment value at low temperature, indicative of the antiferromagnetic coupling of medium size (-55 to -22 cm(-1)). For these systems resembling a compressed prism the coupling constant in walls J4 correlates with the averaged bonding angles in walls alpha: J4 vs. a develops approximately according to a straight line.
DOI http://dx.doi.org/10.1039/c7dt00957g
ISBN
Publisher ROYAL SOC CHEMISTRY
Book Title
ISSN 1477-9226
EISSN 1477-9234
Conference Name
Bibtex ID ISI:000403436200014
Observations
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