Modular Assembly of Isostructural Mixed-Ligand Uranyl Coordination Polymers Based on a Patterning Strategy.

Abstract

Controlling the orderly assembly of molecular building blocks for the formation of the desired architectural, chemical, and physical properties of the resulting solid-state materials remains a long-term goal and deserves to be examined. In this work, we propose a patterning strategy for modular assembly and structural regulation of mixed-ligand uranyl coordination polymers (CPs) through the combination of couples of organic ligands with complementary molecular geometry and well-matched coordination modes. By using a 5-(p-tolyldiazenyl)isophthalic acid ligand (H2ptdi) with different rigid linear bicarboxylic acid linkers to construct a well-defined ladder-like pattern, five novel isostructural uranyl coordination polymers, [(UO)2(ptdi)(bdc)0.5](dma) (1), [(UO)2(ptdi)(bpdc)0.5](dma) (2), [(UO)2(ptdi)(tpdc)0.5](dma) (3), [(UO)2(ptdi)(ndc)0.5](dma) (4), and [(UO)2(ptdi) (pdc)0.5](dma) (5) {H2bdc, 1,4-dicarboxybenzene; H2bpdc, 4,4'-biphenyldicarboxylic acid; H2tpdc, terphenyl-4,4″-dicarboxylic acid; H2ndc, 2,6-naphthalenedicarboxylic acid; H2pdc, 1,6-pyrenedicarboxylic acid; [dma]+, [(CH3)2NH2]+}, were successfully synthesized. Structural analysis reveals that 1-5 have similar ladder-like units but different sizes of one-dimensional nanochannels and interlayer spacing due to the different lengths and widths of the linkers. Because of the changes in interlayer spacing of these isostructural cationic frameworks, differences in the performance of Eu3+ ion exchange with [dma]+ are observed. Moreover, those compounds with high phase purity have been further characterized by thermogravimetric analysis, infrared spectroscopy, and luminescence spectroscopy, element analysis, PXRD and UV spectroscopy. Among them, compound 3 with strong fluorescence can selectively detect Fe3+ over several competing metal cations in aqueous solution. This work not only provides a feasible patterning method for effectively regulating the modular synthesis of functional coordination polymers but also enriches the library of uranyl-based coordination polymers with intriguing structures and functionality.