Anionic Metal–Organic Frameworks of Bismuth Benzenedicarboxylates: Synthesis, Structure and Ligand‐Sensitized Photoluminescence

Abstract

AbstractFour organic–inorganic bismuth benzenedicarboxylate (bdc)frameworks, [Bi(1,4‐bdc)2(dmf)]·(dma)(dmf)2 (1), [Bi(1,4‐bdc)2]·(dma)(dmf) (2), [Bi4(1,4‐bdc)7(HIm)]·(dma)2(dmf)2 (3) and [Bi(1,4‐bdc)2]·(dma) (4) (where dma = dimethyl ammonium cation, HIm = imidazole and dmf = dimethylformamide) have been synthesized under solvothermal conditions, and their structures were determined by single‐crystal X‐ray diffraction. Compound 1 has a layer structure, whereas compounds 2–4 have three‐dimensional structures. All four frameworks are anionic and contain dma cations within cavities in their structures. Compounds 1–3 also contain coordinated and/or guest dmf molecules. The topologies of compounds 1–3 have 4‐connecting nodes; the layer structure in 1 is a corrugated (4,4)‐connected square lattice, but the three‐dimensional structures of 2 and 3 adopt the (dia) net topology. Compound 4 has a 6‐connecting node with a (pcu) net topology. The BiOn polyhedra are hemidirected with a stereochemically active lone pair of electrons in 2, but holodirected with astereochemically inactive lone pair of electrons in 1, 3 and 4. Tb3+‐ and Eu3+‐doped and co‐doped 3 and 4 emit intense, ligand‐sensitized green, red or orange luminescence, respectively.