A New Triazine-Based Tricompartmental Ligand for Stepwise Assembly of Mononuclear, Dinuclear, and 1D-Polymeric Heptacoordinate Manganese(II)/Azido Complexes

作者：Das Animesh; Demeshko Serhiy; Dechert Sebastian; Meyer Franc^*

来源：European Journal of Inorganic Chemistry, 2011, (8): 1240-1248.

DOI：10.1002/ejic.201001104

• Manganese
• Azides
• N ligands
• Magnetic properties
• Coordination polymer

A new ligand 2,4,6-tris[{N-methyl-N`-(pyridine-2-yl)methylidene}hydrazino]-1,3,5-triazine (L) has been synthesized from cyanuric chloride in two steps. The threefold symmetric L features three potentially tridentate {N(3)} binding compartments. However, with Mn(II) it binds a single metal ion using one of the triazine N atoms and two chelate arms. This {N(5)} set forms the equatorial plane of a distorted pentagonal-bipyramidal metal ion environment, with a variety of ligands in axial positions. Five such MnII complexes have been isolated and characterized by X-ray crystallography. Complex 1 features axial water and nitrato-O ligands. In 5, the latter is replaced by dicyanamide. Two terminal azido ligands are found in 3. Depending on the ratio of L:Mn(II):azide, L may also adopt a bridging mode to give the dimeric species [{(H(2)O) Mn(II)L}(mu-1,3-N(3)){LMn(II)(NO(3))}](NO(3))(2) (2) or a 1D coordination polymer [(LMn(II))(mu-1,3-N(3))](n)(NO(3))(n) (4). The basic {LMnII} entity undergoes little structural variation in the series of complexes, which can be viewed as structural snapshots for the assembly of a Mn(II)/azido polymeric chain from well-defined mononuclear building units. Magnetic coupling along the mu-1,3-azido linkage in the dimeric and 1D-extended complexes is weakly antiferromagnetic; the strength of the coupling is rationalized on the basis of the Mn-N-N angles and the dihedral angle tau along the azide ligand.

• 出版日期2011-3