Exploring Crystal Engineering for Porous Uranyl–Organic Frameworks: Insight into Hydrolysis and In Situ Reaction, Structural Variation‐Dependent Physical Properties

Abstract

AbstractThree porous uranyl complexes {(CH3)2NH2[(UO2)(L1)]⋅H2O}n (1), {[(UO2)5(μ2‐OH)(μ3‐OH)(L2)2(H2O)3]}n (2) and {[(UO2)4(μ3‐OH)2(L3*)3]}n (3), {H3L1 = 5‐((4‐carboxybenzyl)oxy)isophthalic acid, H4L2 = 4,4’‐oxydiphthalic acid, and H2L3 = 4,4’‐((6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(azanediyl))dibenzoic acid}, have been designed and synthesized under solvothermal and hydrothermal reaction conditions. All of these ligands are firstly used in the syntheses of uranyl hybrid materials. We investigated the main factors on the uranyl hydrolysis systematically and discussed the in situ reaction mechanism in detail. Furthermore, physical properties of these uranyl complexes are dependent on structural variations, such as unusual solvent‐impressionable five‐peak photoluminescence for 2, surface photoelectric behavior as potential p‐type semiconductors for 2 and 3, and the remarkable superiorities toward selective removal of dye pollutant for the anionic framework 1 compared with the neutral ones 2 and 3.