TY - JOUR
T1 - Crystal structures and magnetic behaviors of cyanido-bridged dinuclear dimetallic systems involving 3d-3d or 3d-5d metal centers
AU - Jae, Il Kim
AU - Jung, Hee Yoon
AU - Hyun, Young Kwak
AU - Eui, Kwan Koh
AU - Chang, Seop Hong
PY - 2008/6
Y1 - 2008/6
N2 - Three cyanido-bridged FeIII-MnII dimers, [Fe(pzcq)(CN)3]-[Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8-(pyrazine-2-carboxamido)quinoline anion, phen = 1,10-phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)] ·MeOH [3; mpzcq = 8-(5-methylpyrazine-2-carboxamido)quinoline anion], and one WV-MnII dinuclear system, [W(bpy)(CN) 6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′-bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]-, [Fe(mpzcq)-(CN)3] -, and [W(bpy)(CN)6]-, with Mn(phen) 2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a -Δ-Λ- Δ-Λ- sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π-π contacts, which eventually lead to the formation of two-dimensional frameworks (1-3) and a one-dimensional chain structure (4). Magnetic analyses of the FeIII-MnII dinuclear systems (1-3) reveal that a shorter Mn-N(cyanide) bond and a more linear Mn-N-C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d-5d magnetic coupling in 4 is stronger than the 3d-3d coupling in 1-3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital.
AB - Three cyanido-bridged FeIII-MnII dimers, [Fe(pzcq)(CN)3]-[Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8-(pyrazine-2-carboxamido)quinoline anion, phen = 1,10-phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)] ·MeOH [3; mpzcq = 8-(5-methylpyrazine-2-carboxamido)quinoline anion], and one WV-MnII dinuclear system, [W(bpy)(CN) 6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′-bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]-, [Fe(mpzcq)-(CN)3] -, and [W(bpy)(CN)6]-, with Mn(phen) 2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a -Δ-Λ- Δ-Λ- sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π-π contacts, which eventually lead to the formation of two-dimensional frameworks (1-3) and a one-dimensional chain structure (4). Magnetic analyses of the FeIII-MnII dinuclear systems (1-3) reveal that a shorter Mn-N(cyanide) bond and a more linear Mn-N-C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d-5d magnetic coupling in 4 is stronger than the 3d-3d coupling in 1-3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital.
KW - Crystal structure
KW - Cyanides
KW - Dinuclear complexes
KW - Magnetism
KW - N ligands
UR - http://www.scopus.com/inward/record.url?scp=53249147529&partnerID=8YFLogxK
U2 - 10.1002/ejic.200800232
DO - 10.1002/ejic.200800232
M3 - Article
AN - SCOPUS:53249147529
SN - 0365-9496
SP - 2756
EP - 2763
JO - Berichte der deutschen chemischen Gesellschaft
JF - Berichte der deutschen chemischen Gesellschaft
IS - 17
ER -