Mixed-valence manganese carboxylate clusters, {MnIII6MnII4}, {MnIII7MnII5Na}, and {MnIII7MnII5}, derived from the combined use of Di-2-pyridyl ketone with selected aliphatic diols
Date
2024-04-22Author
Skordi, KaterinaAlexandropoulos, Dimitris I.
Fournet, Adeline D.
Panagiotou, Nikos
Perlepes, Spyros P.
Christou, George
Tasiopoulos, Anastasios J.
ISSN
1434-1948Publisher
John Wiley & Sons LtdPlace of publication
WeinheimSource
European journal of inorganic chemistryVolume
27Issue
12Pages
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Abstract
Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2 (1), Na[Mn12O2(OH)3(OMe){(py)2C(O)2}6{(py)2C(OH)(O)}2(MeCO2)2(H2O)10](ClO4)8 (2) and [Mn12O4(OH)2{(py)2C(O)2}6{(py)2C(OMe)(O)}(MeCO2)3(NO3)3(H2O)(DMF)2](NO3)2 (3) were prepared from the combination of di-2-pyridyl ketone, (py)2CO, with the aliphatic diols (1,3-propanediol (pdH2) or 1,4-butanediol (1,4-bdH2)) in Mn carboxylate chemistry. The reported compounds do not include the aliphatic diols employed in this reaction scheme; however, their use is essential for the formation of 1–3. The crystal structures of 1–3 are based on multilayer cores which, to our knowledge, are reported for the first time in Mn cluster chemistry. Direct current (dc) magnetic susceptibility studies showed the presence of dominant antiferromagnetic exchange interactions within 1–3. Alternating current (ac) magnetic susceptibility studies revealed the presence of out-of-phase signals below 3.0 K for 2 and 3 indicating the slow relaxation of the magnetization vector, characteristic of single-molecule magnets; the Ueff value of 2 was found to be 23 K and the preexponential factor τ0 ~7.6×10−9 s.
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