Novel Inorganic–Organic Hybrid Frameworks of Manganese(II): Syntheses, Crystal Structures, and Physical Properties

Abstract

Three new inorganic–organic hybrid frameworks, [Mn 2(BPTCA)(phen) 2·H 2O] n ( 1), [Mn 4(BPTCA) 2(H 2O) 10·2.5H 2O] n ( 2), and [Mn 2(BPTCA)(μ 2-H 2O) 2] n ( 3) (BPTCA 4− = 4,4′-bipyridine-2,2′,6,6′-tetracarboxylate; phen = 1,10-phenanthroline), have been synthesized under hydrothermal conditions. Complex 1 is a two-dimensional (2D) network constructed by infinite O−Mn−O−C−O−Mn- chains and BPTCA 4− ligands, and an intriguing slide fastener-like three-dimensional (3D) framework structure is formed by the π···π interactions between the phen molecules. Complex 2 crystallized in a chiral space group P2 1 has a 2D network structure formed by Mn 4 cluster units and BPTCA 4− linkers, while complex 3 obtained at higher temperature than 2 is a 3D porous architecture. The result implies that the hydrothermal reaction temperature has a great influence on the structure of the complexes in this system. The magnetic behaviors of the complexes have been investigated and 2 showed modest powder second harmonic generation activity.