TY  - JOUR
AU  - Dulcevscaia, G.M.
AU  - Filippova, I.G.
AU  - Speldrich, M.
AU  - Leusen, J. van
AU  - Kravtsov, V.C.
AU  - Baca, S.G.
AU  - Kögerler, P.
AU  - Liu, S.-X.
AU  - Decurtins, S.
TI  - Cluster-based Networks: 1D and 2D Coordination Polymers Based on {MnFe2(µ3-O)}-type Clusters
JO  - European journal of inorganic chemistry
VL  - 51
SN  - 1434-1948
CY  - Weinheim
PB  - Wiley-VCH
M1  - PreJuSER-22291
SP  - 5110 -5117
PY  - 2012
N1  - Financial support from the Swiss National Science Foundation (SCOPES IZ73Z0_127925), the German Federal Ministry of Education and Research (project MDA 08/022), the Academy of Sciences of Moldova (project No. 09.820.05.10GF), the Supreme Council for Science and Technological Development of the Republic of Moldova (projects 09.836.05.02A and 11.817.05.03A), and the EU (POLYMAG, IIF contract no. 252984) are acknowledged. We thank Prof. H. Stoeckli-Evans for the collection of crystallographic data sets for compound 1.
AB  - A straightforward approach to heterometallic Mn-Fe cluster-based coordination polymers is presented. By employing a mixed-valent μ(3)-oxo trinuclear manganese(II/III) pivalate cluster, isolated as [Mn(II)Mn(III)(2)O(O(2)CCMe(3))(6)(hmta)(3)]·(solvent) (hmta = hexamethylenetetramine; solvent = n-propanol (1), toluene (2)) in the reaction with a μ(3)-oxo trinuclear iron(III) pivalate cluster compound, [Fe(3)O(O(2)CCMe(3))(6)(H(2)O)(3)]O(2)CCMe(3)·2Me(3)CCO(2)H, three new heterometallic {Mn(II)Fe(III)(2)} cluster-based coordination polymers were obtained: the one-dimensional polymer chain compounds {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(2)]·0.5MeCN}(n) (3) and {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(2)]·Me(3)CCO(2)H·(n-hexane)}(n) (4) and the two-dimensional layer compound {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(1.5)]·(toluene)}(n) (5). Single-crystal X-ray diffraction analysis reveals a μ(3)-oxo trinuclear pivalate cluster building block as the main constituent in all polymer compounds. Different M:hmta ratios in 1-5 are related to the different structural functions of the N-containing ligand. In clusters 1 and 2, three hmta ligands are monodentate, whereas in chains 3 and 4 two hmta ligands act as bridging ligands and one is a monodentate ligand; in 5, all hmta molecules act as bidentate bridges. Magnetic studies indicate dominant antiferromagnetic interactions between the metal centers in both homometallic {Mn(3)}-type clusters 1 and 2 and heterometallic {MnFe(2)}-type coordination polymers 3-5. Modeling of the magnetic susceptibility data to a isotropic model Hamiltonian yields least-squares fits for the following parameters: J(1)(Mn(II)-Mn(III)) = -6.6 cm(-1) and J(2)(Mn(III)-Mn(III)) = -5.4 cm(-1) for 1; J(1) = -5.5 cm(-1) and J(2)(Mn(III)-Mn(III)) = -3.9 cm(-1) for 2; J(1)(Mn(II)-Fe(III)) = -17.1 cm(-1) and J(2)(Fe(III)-Fe(III)) = -43.7 cm(-1) for 3; J(1) = -23.8 cm(-1) and J(2) = -53.4 cm(-1) for 4; J(1) = -13.3 cm(-1) and J(2) = -35.4 cm(-1) for 5. Intercluster coupling plays a significant role in all compounds 1-5.
KW  - J (WoSType)
LB  - PUB:(DE-HGF)16
C6  - pmid:22524248
UR  - <Go to ISI:>//WOS:000303952900032
DO  - DOI:10.1021/ic202644t
UR  - https://juser.fz-juelich.de/record/22291
ER  -