3D Uranyl Organic Frameworks Supported by Rigid Octadentate Carboxylate Ligand: Synthesis, Structure Diversity, and Luminescence Properties

Abstract

Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH 4 ][(UO 2 ) 3 (HTTDS)(H 2 O)] (1), [(UO 2 ) 4 (HTTDS) 2 ](HIM) 6 (2, IM = imidazole), [(UO 2 ) 4 (TTDS)(H 2 O) 2 (Phen) 2 ] (3, Phen = 1,10-phenanthroline), [Zn(H 2 O) 4 ] 0.5 [(UO 2 ) 3 (HTTDS)(H 2 O) 4 ] (4), and {(UO 2 ) 2 [Zn-(H 2 O) 3 ] 2 (TTDS)} (5), {Zn(UO 2 ) 2 (H 2 O)(Dib) 0.5 (HDib)(HTTDS)} (6, Dib = 1,4-di(1H-imidazol-1-yl)benzene) and [Na]{(UO 2 ) 4 [Cu 3 (u 3 -OH)(H 2 O) 7 ](TTDS) 2 } ( 7) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5dicarboxyphenyl)silicon(H 8 TTDS). These UOFs have different 3D self-assembled structures as a function of co-ligands, structure-directing agents and transition metals. The structure of 1 has an infinite ribbon formed by the UO 7 pentagonal bipyramid bridged by carboxylate groups. With further introduction of auxiliary N-donor ligands, different structure of 2 and 3 are formed, in 2 the imidazole serves as space filler, while in 3 the Phen are bound to [UO 2 ] 2 + units as coligands. The second metal centers were introduced in the syntheses of 4-7, and in all cases, they are part of the final structures, either as a counterion (4) or as a component of framework (5 À 7). Interesting, in 7, a rare polyoxometalate [Cu 3 (μ 3 -OH)O 7 (O 2 CR) 4 ] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO 2 ) 2 (O 2 CR) 4 ] unit. Those uranyl carboxylates were sufficiently determined by single crystal X-ray diffraction, and their topological structures and luminescence properties were analyzed in detail.

Regulating the Porosity of Uranyl Phosphonate Frameworks with Quaternary Ammonium: Structure, Characterization, and Fluorescent Temperature Sensors

“…Metal–organic frameworks (MOFs) based on coordination chemistry with more porous structures are featured by designability, making the structures and functions integrated into an extreme periodic lattice matrix at an atomic-level scale and providing more space for material design. , Both inorganic building units and organic ligands can be tailored by choosing proper metal ions and organic groups to create novel compounds for various applications, such as sensors, proton conductors, , molecular separation, − or heterogeneous catalysts. , Uranium-based MOFs (UMOFs) stand out among many actinides as the most studied ones due to their excellent optical properties. , As one of the essential elements for nuclear science and technology, uranium plays a crucial role in the nuclear fuel cycle process. Therefore, understanding uranium’s physical and chemical properties are fundamental to reducing radioactive waste and raising the level of the chemical process to make nuclear energy safer, more efficient, and sustainable .…”

“…9,10 Uranium-based MOFs (UMOFs) stand out among many actinides as the most studied ones due to their excellent optical properties. 11,12 As one of the essential elements for nuclear science and technology, uranium plays a crucial role in the nuclear fuel cycle process. Therefore, understanding uranium's physical and chemical properties are fundamental to reducing radioactive waste and raising the level of the chemical process to make nuclear energy safer, more efficient, and sustainable.…”

Chain, Network and Framework Formation in Uranyl Ion Complexes with 1,1′‐Biphenyl‐3,3′,4,4′‐Tetracarboxylate

“…Taking a broader viewpoint, an eclectic selection from the recent literature [13,[48][49][50][51][52][53] illustrates that the solid state coordination chemistry of uranyl carboxylates continues to be an active area of research concerned with a variety of possible applications. In our own work in this area, largely focussed on anionic coordination polymers, it has been apparent that hydrogen bonding interactions can have a major influence on the form of the complexes and even upon the coordination sphere of the uranyl ion.…”