TY - JOUR
T1 - A new MnII4MnIII4 cluster from the use of methyl 2-pyridyl ketone oxime in manganese carboxylate chemistry
T2 - Synthetic, structural and magnetic studies
AU - Stoumpos, Constantinos C.
AU - Stamatatos, Theocharis C.
AU - Psycharis, Vassilis
AU - Raptopoulou, Catherine P.
AU - Christou, George
AU - Perlepes, Spyros P.
N1 - Funding Information:
This work was supported by EPEAEK II (Program PYTHAGORAS I, Grant b.365.037 to S.P.P) and NSF (CHE-0414555 to G.C.).
Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2008/12/12
Y1 - 2008/12/12
N2 - The use of methyl 2-pyridyl ketone oxime (mpkoH) in manganese benzoate chemistry is reported. The reaction of Mn(O2CPh)2 · 2H2O with two equivalents of mpkoH in CH2Cl2 affords the mononuclear complex [MnII(O2CPh)2(mpkoH)2] (2) in high yield. The MnII atom is coordinated by two monodentate PhCO2- groups and two N,N′-bidentate mpkoH chelates in a cis-cis-trans fashion. Reaction mixtures comprising (NBun4)[MnIII4O 2(O2CPh)9(H2O)] and mpkoH in CH2Cl2, [MnIIMnIII2O(O2CPh) 6(py)2(H2O)] and mpkoH in CH2Cl2, or Mn(O2CPh)2 · 2H2O, NBun4 MnO4 and mpkoH in MeOH/MeCN/CH2Cl2 all lead to the mixed-valent cluster [MnII4MnIII4O2(OH )2(O2CPh)10(mpko)4] (3) in moderate yields. The cluster molecule has the [Mn8(μ4-O)2(μ3-OH) 2]14+ core (another description of the core is [Mn8(μ4-O)2(μ3-OH) 2(μ-OR′′)4(μ-ONR‴) 4]6+). Peripheral ligation is provided by two η1, four η1:η1:μ and four η1:η2:μ3PhCO2 - groups, as well as four η1:η1:η1:μ mpko- ligands. Variable-temperature, solid-state dc and ac magnetic studies were carried out on complex 3 in the 5.0-300 K (dc) and 1.8-10 K (ac) ranges. The data reveal dominant antiferromagnetic interactions and a resulting S = 0 ground state, which is rationalized in terms of the strong antiferromagnetic coupling within the central {Mn2III O2}2+ subunit.
AB - The use of methyl 2-pyridyl ketone oxime (mpkoH) in manganese benzoate chemistry is reported. The reaction of Mn(O2CPh)2 · 2H2O with two equivalents of mpkoH in CH2Cl2 affords the mononuclear complex [MnII(O2CPh)2(mpkoH)2] (2) in high yield. The MnII atom is coordinated by two monodentate PhCO2- groups and two N,N′-bidentate mpkoH chelates in a cis-cis-trans fashion. Reaction mixtures comprising (NBun4)[MnIII4O 2(O2CPh)9(H2O)] and mpkoH in CH2Cl2, [MnIIMnIII2O(O2CPh) 6(py)2(H2O)] and mpkoH in CH2Cl2, or Mn(O2CPh)2 · 2H2O, NBun4 MnO4 and mpkoH in MeOH/MeCN/CH2Cl2 all lead to the mixed-valent cluster [MnII4MnIII4O2(OH )2(O2CPh)10(mpko)4] (3) in moderate yields. The cluster molecule has the [Mn8(μ4-O)2(μ3-OH) 2]14+ core (another description of the core is [Mn8(μ4-O)2(μ3-OH) 2(μ-OR′′)4(μ-ONR‴) 4]6+). Peripheral ligation is provided by two η1, four η1:η1:μ and four η1:η2:μ3PhCO2 - groups, as well as four η1:η1:η1:μ mpko- ligands. Variable-temperature, solid-state dc and ac magnetic studies were carried out on complex 3 in the 5.0-300 K (dc) and 1.8-10 K (ac) ranges. The data reveal dominant antiferromagnetic interactions and a resulting S = 0 ground state, which is rationalized in terms of the strong antiferromagnetic coupling within the central {Mn2III O2}2+ subunit.
KW - Crystal structures
KW - Magnetochemistry
KW - Manganese benzoate chemistry
KW - Methyl 2-pyridyl ketone oxime metal complexes
KW - Mixed-valent manganese clusters
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U2 - 10.1016/j.poly.2008.09.010
DO - 10.1016/j.poly.2008.09.010
M3 - Article
AN - SCOPUS:56849088975
VL - 27
SP - 3703
EP - 3709
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 18
ER -