Auxiliary Ligand-Dependent Adaptive Regulation of Uranyl Coordination in Mixed-Ligand Uranyl Compounds of Flexible Biphenyltetracarboxylic Acid.

Abstract

The mixed-ligand strategy is one of the important methods for preparing new materials and regulating the properties of materials. In this work, by introducing different auxiliary ligands (ALs), we have obtained a series of mixed-ligand uranyl complexes (1-6) from a flexible biphenyltetracarboxylic acid (H4bptc) with an adjustable orthogonal conformation and studied the influence of different organic base molecules on the coordination and assembly of H4bptc with a uranyl cation. It is found that the coordinated ALs, including 4,4'-bipyridine-1,1'-dioxide and 1,10-phenanthroline, partially occupy the coordination sites of the uranyl center and directly affect the molecular conformations and uranyl coordination of flexible bptc linkers. On the other hand, noncoordinated ALs such as protonated 4,4'-bipyridine ([H2(4,4'-bpy)]2+) or dimethylammonium, which work as counterions in the form of encapsulated guests or hydrogen-bonded templates, also have a nonnegligible impact on the conformation and coordination of bptc linkers. Most interestingly, the AL-mediated evolution of uranyl coordination by the bptc linker and coordination geometry of the uranyl center is clearly observed, which suggests the adaptability of flexible bptc linkers to take suitable molecular configurations and uranyl coordination modes so as to adapt to the external regulator agents and varying environment. The physicochemical characterization of these uranyl compounds, especially photoluminescence, is addressed and discussed, and the results reveal that compound 5 has the potential to serve as a multifunctional radiation detection material for UV light and X-ray radiation.