title: Cyanide-bridged Fe(III)-Mn(III) bimetallic systems assembled from the fac-Fe tricyanide and Mn Schiff bases: structures, magnetic properties, and density functional theory calculations.
abstract: Reaction of [(Tp)Fe(CN)(3)](-) [Tp = hydrotris(pyrazolyl)borate] with respective Mn(III) Schiff bases led to the formation of four dimeric molecules, [(Tp)Fe(CN)(3)][Mn(1-napen)(H(2)O)].MeCN.4H(2)O [1; 1-napen = N,N'-ethylenebis(2-hydroxy-1-naphthylideneiminato) dianion], [(Tp)Fe(CN)(3)][Mn(5-Clsalen)(H(2)O)] [2; 5-Clsalcy = N,N'-(trans-1,2-cyclohexanediylethylene)bis(5-chlorosalicylideneiminato) dianion], [(Tp)Fe(CN)(3)][Mn(2-acnapen)(MeOH)].MeOH [3; 2-acnapen = N,N'-ethylenebis(1-hydroxy-2-acetonaphthylideneiminato) dianion], [(Tp)Fe(CN)(3)][Mn(3-MeOsalen)(H(2)O)] [4; 3-MeOsalen = N,N'-ethylenebis(3-methoxysalicylideneiminato) dianion], and a one-dimensional (1D) zigzag chain [(Tp)Fe(CN)(3)][Mn(2-acnapen)].H(2)O (5). The dimers contain multiple intermolecular interactions such as hydrogen bonds, face-to-face pi-pi contacts, and edge-to-face CH-pi forces, raising molecular dimensions from one-dimensional (1D) up to three-dimensional (3D) arrays, whereas there are no pi-pi stacking interactions in the 1D chain compound. Magnetic measurements reveal that ferromagnetic couplings are obviously operative between Mn(III) and Fe(III) spin centers transmitted by CN bridges for 1-3 and 5, and antiferromagnetic interactions are however unexpectedly present in 4. On the basis of the proper spin Hamiltonians, magnetic exchange couplings are estimated to be in the span from 1.79 to 7.48 cm(-1) for the ferromagnetically coupled systems and -1.40 cm (-1) for the antiferromagnetic dimer. A slow magnetic relaxation is tangible in 5, which is in connection with isolated chains devoid of any intermolecular noncovalent interactions. Density Functional Theory (DFT) calculations and comparison of structural parameters suggest that the observed magnetic behaviors are mainly associated with the bending of the Mn-N[triple bond]C angle in the bridging pathway.
authors.affiliation: Department of Chemistry (BK21), Korea University, Seoul 136-713, Korea.
authors.forename: Hyun Young
authors.initials: HY
authors.lastname: Kwak
authors.forename: Dae Won
authors.initials: DW
authors.lastname: Ryu
authors.forename: Jin Wuk
authors.initials: JW
authors.lastname: Lee
authors.forename: Jung Hee
authors.initials: JH
authors.lastname: Yoon
authors.forename: Hyoung Chan
authors.initials: HC
authors.lastname: Kim
authors.forename: Eui Kwan
authors.initials: EK
authors.lastname: Koh
authors.forename: Jamin
authors.initials: J
authors.lastname: Krinsky
authors.forename: Chang Seop
authors.initials: CS
authors.lastname: Hong
mesh_terms: D007501:Iron / Q000737:chemistry*; D008280:Magnetics; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D012545:Schiff Bases / Q000737:chemistry
chemical_list: D009570:Nitriles; D009942:Organometallic Compounds; D012545:Schiff Bases; D008345:Manganese; D007501:Iron