TY - JOUR
T1 - Tetranuclear [Mn2Co2], [Mn2Fe 2], and [Mn2Mn2] complexes with defective double-cubane cores and phenoxo and oxo bridges
T2 - Syntheses, crystal structures, and electronic properties
AU - Malpaharia, Pijush
AU - Pramanik, Koushik
AU - Costes, Jean Pierre
AU - Tuchagues, Jean Pierre
AU - Moulton, Brian
AU - Zaworotko, Michael J.
AU - Das, Babulal
AU - Chandra, Swapan K.
PY - 2014/8
Y1 - 2014/8
N2 - Three new tetranuclear complexes [MnIII2Co III2O2(L)2][ClO4] 2 (1), [MnIII2FeIII 2O2(L)2][ClO4]2 (2), and [MnIII2MnIII2O2(L) 2][MnII(NCS)4] (3) have been synthesized through reactions of the mononuclear [MnIIIL] precursor with the corresponding metal perchlorate under aerobic conditions [H3L = tris(2-salicylaldimine)amine, a condensation product between tris(2-aminoethyl)amine and salicylaldehyde in a 1:3 molar ratio]. These compounds have been characterized by spectroscopic and analytical techniques including single-crystal X-ray structure analysis, electron paramagnetic resonance (EPR) spectroscopy, Mössbauer spectroscopy, and magnetic measurements. The structure of 1 consists of oxo-/phenoxo-bridged Co III and MnIII centers in a defective double-cubane topology. The molecules of 2 and 3 have similar structures with the Co III centers changed to FeIII centers in 2 and to Mn III centers in 3. These isostructural complexes have been scrutinized with regard to changes in distortions (distances and angles) of the metal coordination spheres. Magnetic studies indicate that 1, 2, and 3 show predominant antiferromagnetic interactions. Changes in the electronic properties concomitant with changes in the distortions in 1, 2, and 3 are analyzed in terms of magnetostructural correlations.
AB - Three new tetranuclear complexes [MnIII2Co III2O2(L)2][ClO4] 2 (1), [MnIII2FeIII 2O2(L)2][ClO4]2 (2), and [MnIII2MnIII2O2(L) 2][MnII(NCS)4] (3) have been synthesized through reactions of the mononuclear [MnIIIL] precursor with the corresponding metal perchlorate under aerobic conditions [H3L = tris(2-salicylaldimine)amine, a condensation product between tris(2-aminoethyl)amine and salicylaldehyde in a 1:3 molar ratio]. These compounds have been characterized by spectroscopic and analytical techniques including single-crystal X-ray structure analysis, electron paramagnetic resonance (EPR) spectroscopy, Mössbauer spectroscopy, and magnetic measurements. The structure of 1 consists of oxo-/phenoxo-bridged Co III and MnIII centers in a defective double-cubane topology. The molecules of 2 and 3 have similar structures with the Co III centers changed to FeIII centers in 2 and to Mn III centers in 3. These isostructural complexes have been scrutinized with regard to changes in distortions (distances and angles) of the metal coordination spheres. Magnetic studies indicate that 1, 2, and 3 show predominant antiferromagnetic interactions. Changes in the electronic properties concomitant with changes in the distortions in 1, 2, and 3 are analyzed in terms of magnetostructural correlations.
KW - Cobalt
KW - Heterometallic complexes
KW - Iron
KW - Magnetic properties
KW - Manganese
UR - http://www.scopus.com/inward/record.url?scp=84905492631&partnerID=8YFLogxK
U2 - 10.1002/ejic.201402191
DO - 10.1002/ejic.201402191
M3 - Article
AN - SCOPUS:84905492631
SN - 1434-1948
SP - 3527
EP - 3535
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 22
ER -