A series of manganese-carboxylate coordination polymers exhibiting diverse magnetic properties

Dalton Trans. 2008 Oct 21:(39):5350-7. doi: 10.1039/b808691e. Epub 2008 Aug 21.

Abstract

The hydrothermal reactions of an asymmetrical 4-(4-carboxyphenylamino)-3,5-dinitrobenzoic acid (H2cpdba), MnCl2.4H2O, or together with 2,2'-bipyridine (2,2'-bpy) or 4,4'-bipyridine (4,4'-bpy) afford three novel molecule-based magnetic coordination polymers [Mn(cpdba)]n (1), ([Mn2(cpdba)2(2,2'-bpy)2(H2O)2].H2O)n (2) and ([Mn2(cpdba)2(4,4'-bpy)].2H2O)n (3). Compound 1 has a 3D acentric coordination network containing carboxylate-bridged 1D ladder-like manganese chains with spin-canted antiferromagnetism (J = -3.51 cm(-1) for the coupling along the ladder legs, and zJ' = 0.22 cm(-1) for coupling along the ladder rungs), whereas compounds 2 and 3 crystallize in the centrosymmetric space groups P1 and C2/c, respectively. 2 exhibits a 1D chain structure, which is extended into a 3D supramolecular network by pi-pi stacking interactions, while 3 features a quite complex 3D network built up from the cpdba(2-) and 4,4'-bpy spacers as well as the carboxylate-bridged Mn(II) chains. Both 2 and 3 show weak antiferromagnetic coupling interactions (J = -0.55 cm(-1) for 2), and a field-induced spin-flop magnetic transition can also be observed in 2 at ca. 3.2 T at 2 K.