Details make the difference: a family of tetranuclear CuIIMnIII complexes with cube-like and double open cube-like cores. Issue 23 (31st May 2017)

• Record Type: Journal Article
• Authors: Stetsiuk, Oleh; Nesterova, Oksana V.; Kokozay, Vladimir N.; Domasevitch, Kostiantyn V.; Omelchenko, Iryna V.; Shishkin, Oleg V.; Vranovičová, Beata; Boča, Roman; Pombeiro, Armando J. L.; Petrusenko, Svitlana R.
• Is Part Of: Dalton transactions. Volume 46:Issue 23(2017)
• Page Start: 7480
• Page End: 7494
• Publication Date: 2017-05-31
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00957g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Syntheses, crystal structures and magnetostructural correlations of novel Cu II Mn III complexes are discussed. Abstract : The "direct synthesis" approach, namely one-pot reaction of metal powders and ammonium salt with a methanol solution of a polydentate Schiff base (H2 L) formed in situ from salicylaldehyde and ethanolamine, has been successfully used for the preparation of the new heterometallic compounds [Cu3 Mn(L)4 (CH3 OH)3 ]I3 (1 ), [Cu3 Mn(L)4 (CH3 OH)3 (H2 O)]NCS·H2 O (2 ), [Cu3 Mn(L)4 (CH3 OH)(H2 O)2.55 ]Br·0.45H2 O (3 ) and [Cu3 Mn(L)4 (H2 O)3.4 ]BF4 ·0.6H2 O (4 ). Crystallographic analysis revealed that1–4 are based on the tetranuclear core {CuII3Mn III (μ3 -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 [Cu3 Mn(L)4 (CH3 OH)3 ]2 [Mn(NCS)4 ]·2CH3 OH (5 ) has been obtained by the "building block" approach using the reaction of [Cu(HL)2 ] with manganese acetate and NH4 NCS in methanol. The crystal structure of5 revealed the {CuII3Mn III (μ-O)2 (μ3 -O)2 } metal core which can be viewed as a double open cube. In spite of a similar {Cu3 MnO4 } atom set in the cores of1–5, the complexes show rather different molecular structures and significantly differ by the number and combinations of coordinated CH3 OH/H2 O solvent molecules. Variable-temperature (2–300 K) magnetic susceptibility along with variable-field magnetization measurements of1–5 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 J 4 correlates with the averaged bonding angles in walls α : J 4 vs. α develops approximately according to a straight line.