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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 681826.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Syntheses, Structures, Magnetic Properties, and Density Functional Theory Magneto-Structural Correlations of Bis(μ-phenoxo) and Bis(μ-phenoxo)-μ-acetate/Bis(μ-phenoxo)-bis(μ-acetate) Dinuclear FeIIINiII Compounds
Authors:Hazra, Susanta; Bhattacharya, Sagarika; Singh, Mukesh Kumar; Carrella, Luca; Rentschler, Eva; Weyhermüller, Thomas; Rajaraman, Gopalan; Mohanta, Sasankasekhar
Language:English
Date of Publication (YYYY-MM-DD):2013
Title of Journal:Inorganic Chemistry
Journal Abbrev.:Inorg. Chem.
Volume:52
Start Page:12881
End Page:12892
Review Status:Peer-review
Audience:Experts Only
Abstract / Description:The bis(mu-phenoxo) (FeNiIII)-Ni-II compound [Fe-III(N-3)(2)LNiII(H2O)(CH3CN)](ClO4) (1) and the bis(mu-phenoxo)-mu-acetate/bis(mu-phenoxo)-bis(mu-acetate) (FeNiII)-Ni-III compound {[Fe-III(OAc)LNiII(H2O)(mu-OAc)](0.6)center dot[(FeLNiII)-L-III(mu-OAc)(2)](0.4)}(ClO4)center dot 1.1H(2)O (2) have been synthesized from the Robson type tetraiminodiphenol macrocyclic ligand H2L, which is the [2 + 2] condensation product of 4-methyl-2,6-diformylphenol and 2,2'-dimethy1-1,3-diaminopropane. Single-crystal X-ray structures of both compounds have been determined. The cationic part of the dinuclear compound 2 is a cocrystal of the two species [Fe-III(OAc)LNiII(H2O)(mu-OAc)](+) (2A) and [(FeLNiII)-L-III(mu-OAc)(2)](+) (2B) with weights of 60% of the former and 40% of the latter. While 2A is a triply bridged bis(mu-phenoxo)-mu-acetate system, 2B is a quadruply bridged bis(mu-phenoxo)-bis(mu-acetate) system. Variable-temperature (2-300 K) magnetic studies reveal antiferromagnetic interaction in 1 and ferromagnetic interaction in 2 with J values of -3.14 and 7.36 cm(-1), respectively (H = -2JS(1)center dot S-2). Broken-symmetry density functional calculations of exchange interaction have been performed on complexes 1 and 2 and also on previously published related compounds, providing good numerical estimates of J values in comparison to experiments. The electronic origin of the difference in magnetic behavior of 1 and 2 has been well understood from MO analyses and computed overlap integrals of BS empty orbitals. The role of acetate and thus its complementarity/countercomplementarity effect on the magnetic properties of diphenoxo-bridged (FeNiII)-Ni-III compounds have been determined on computing J values of model compounds by replacing bridging acetate and nonbridging acetate ligand(s) by water ligands in the model compounds derived from 2A,B. The DFT calculations have also been extended to develop several magneto-structural correlations in these types of complexes, and the correlations focus on the role of Fe-O-Ni bridge angle, average Fe/Ni-O bridge distance, Fe-O-Ni-O dihedral angle, and out-of-plane shift of the phenoxo group.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:Hazra, S.; Bhattacharya, S.; Mohanta, S.; Univ Calcutta, Dept Chem, Kolkata 700009, India.
Singh, M. K.; Rajaraman, G.; Indian Inst Technol, Dept Chem, Bombay 400076, Maharashtra, India.
Carrella, L.; Rentschler, E.; Johannes Gutenberg Univ Mainz, Inst Anorgan Chem & Analyt Chem, D-55128 Mainz, Germany.
Identifiers:ISI:000327225900009 [ID No:1]
ISSN:0020-1669 [ID No:2]
DOI:10.1021/ic400345w
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