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Updated: Feb 2, 2026

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Uranyl-Organic Coordination Compounds Incorporating Photoactive Vinylpyridine Moieties: Synthesis, Structural
Si Wu1,2, Lei Mei1, Fei-Ze Li1
1Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics , Chinese Academy of Sciences , Beijing 100049 , China.
Abstract:
The fluorescence of uranyl originated from electronic transitions (S11-S00 and S10-S0v, v = 0-4) of the ligand-to-metal charge transfer (LMCT) process is an intrinsic property of many uranyl coordination compounds. However, light-induced regulation on fluorescence features of uranyl hybrid materials through photoactive functional groups is less investigated. In this work, the photoactive vinyl group-containing ligands, ( E)-methyl 3-(pyridin-4-yl)acrylate and ( E)-methyl 3-(pyridin-3-yl)acrylate, have been used in the construction of uranyl coordination polymers in the presence of 1,10-phenanthroline (phen). Five compounds (UO2)3(μ3-O)(μ2-OH)2(L1)2( phen)2(1), (UO2)3(μ3-O)(μ2-OH)3(L1)( phen)2 (2), (UO2)3(μ3-O)(μ2-OH)3(L2)( phen)2 (3), [(UO2)2(μ2-OH)2(L2)2( phen)2]·2H2O (4), and (UO2)Zn(SO4)(phen)(H2O)(OH)2(5) were obtained under hydrothermal conditions. Compounds 1-4 are polynuclear uranyl structures with abundant π-π interactions and hydrogen bonds contributed to the 3D crystal packing of them. As model compounds, 1 and 3 are selected for exploring photoresponsive behaviors. The emission intensities of these two compounds are found to decrease gradually over the exposure time of UV irradiation. X-ray single crystal structural analysis suggests that the fluorescence attenuation can be explained by the slight rotation of pyridinyl groups around the carbon-carbon double bond during UV irradiation, which is accompanied by the change of weak interactions, i.e., π-π interactions and hydrogen bonds in strength and density. This feature of light-induced fluorescence attenuation may enable these two compounds to act as potential photoresponsive sensor materials.
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