Journal Article

PreJuSER-22291

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Cluster-based Networks: 1D and 2D Coordination Polymers Based on {MnFe2(µ3-O)}-type Clusters

Dulcevscaia, G. M. ; Filippova, I. G. ; Speldrich, M. ; Leusen, J. v. ; Kravtsov, V. C. ; Baca, S. G. ; Kögerler, P.FZJ* ; Liu, S.-X. ; Decurtins, S.

2012
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1021/ic202644t

Abstract: 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.

Keyword(s): J

Note: 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.

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Contributing Institute(s):

1. Elektronische Eigenschaften (PGI-6)

Research Program(s):

1. Grundlagen für zukünftige Informationstechnologien (P42)
2. POLYMAG - Magnetic Coordination Cluster Polymers (252984) (252984)

Appears in the scientific report 2012

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Database coverage:
; Current Contents - Social and Behavioral Sciences ; JCR ; NCBI Molecular Biology Database ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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