Hydrogencyanamide‐Bridged One‐Dimensional Polymers Built on MnIII–Schiff Base Fragments: Synthesis, Structure, and Magnetism

The ability of NCNH(-) to construct transition metal coordination polymers and to transmit magnetic coupling was investigated. By introduction of various tetradentate Schiff base ligands (L) and different solvents (S), nine NCNH(-)-bridged manganese(III) coordination complexes were obtained. Their structures can be divided into three types: I) NCNH-bridged chains built on mononuclear [Mn(III)(L)] units, [Mn(III)(L)(mu(1,3)-NCNH)](n) (L=5-Brsalen (1), 5-Clsalen (2)); II) NCNH-bridged chains built on dinuclear [Mn(III) (2)(L)(2)] units, complexes 3-8, [Mn(III) (2)(L)(2)(mu(1,3)-NCNH)]ClO(4)S (L=salen, 5-Fsalen, 5-Clsalen, 5-OCH(3)salen; S=CH(3)OH or C(2)H(5)OH); III) NCNH-bridged Mn(III) dimers linked by hydrogen bonds into a 1D polymer, {[Mn(III)(3-OCH(3)salen)(H(2)O)](2)(mu(1,3)-NCNH)}ClO(4) x 0.5 H(2)O (9, salen=N,N'-bis(salicylidene)-1,2-diaminoethane). In these complexes, the N[triple chemical bond]C--NH(-) resonance structure dominates the bonding mode of the NCNH(-) ligand adopting the mu(1,3)-bridging mode. Magnetic characterization shows that the asymmetric NCNH(-) bridge transmits antiferromagnetic interaction between Mn(III) ions and often favors the weak ferromagnetism caused by spin canting in these one-dimensional chains. However, these complexes exhibit different magnetic behaviors at low temperatures.