Bismuth Tri- and Tetraarylcarboxylates: Crystal Structures, In Situ X-ray Diffraction, Intermediates and Luminescence

作者：Feyand Mark; Koeppen Milan; Friedrichs Gernot; Stock Norbert^*

来源：Chemistry - A European Journal, 2013, 19(37): 12537-12546.

DOI：10.1002/chem.201301139

• bismuth
• high-throughput screening
• hydrothermal synthesis
• luminescence
• X-ray diffraction

A systematic investigation of the systems Bi3+/carboxylic acid/HNO3 for the tri- and tetracarboxylic acids pyromellitic acid (H(4)Pyr), trimellitic acid (H(3)Tri) and trimesic acid (H3BTC) acid led to the discovery of five new bismuth carboxylates. Structural characterisation allowed the influence of the linker geometry and the Bi3+:linker molar ratio in the starting solution on the crystal structure to be determined. The crystallisation of three selected compounds was investigated by in situ energy-dispersive X-ray diffraction. Three new crystalline intermediates were observed within minutes, and two of them could be isolated by quenching of the reaction mixture. Their crystal structures were determined from laboratory and synchrotron X-ray powder diffraction data and allowed a possible reaction pathway to be established. In depth characterisation of the luminescence properties of the three bismuth pyromellate compounds was carried out. Fluorescence and phosphorescence could be assigned to (mainly) ligand- and metal-based transitions. The polymorphs of Bi(HPyr) exhibit different luminescence properties, although their structures are very similar. Surprisingly, doping of the three host structures with Eu3+ and Tb3+ ions was only successful for one of the polymorphs.

• 出版日期2013-9-9