Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2(
- Award ID(s):
- 0914935
- NSF-PAR ID:
- 10057206
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 49
- Issue:
- 11
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 4753 to 4755
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract 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 of1 –3 . The crystal structures of1 –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 within1 –3 . Alternating current (ac ) magnetic susceptibility studies revealed the presence of out‐of‐phase signals below 3.0 K for2 and3 indicating the slow relaxation of the magnetization vector, characteristic of single‐molecule magnets; theUeff value of2 was found to be 23 K and the preexponential factorτ0 ~7.6×10−9 s. -
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Abstract Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (
1 , M=Co,2 : M=Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1 and2 in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1 and2 are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [J iso(VIV−VIV)=−5.4(1 ); −3.9(2 ) cm−1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [J iso(VIV−CoII)=−12.6 and −7.5 cm−1] contained in1 .
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/ic1006605
