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

Three new inorganic–organic hybrid frameworks, [Mn 2 (BPTCA)(phen) 2 ·H 2 O] n ( 1 ), [Mn 4 (BPTCA) 2 (H 2 O) 10 ·2.5H 2 O] n ( 2 ), and [Mn 2 (BPTCA)(μ 2 -H 2 O) 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 P 2 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.