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3D Uranyl Organic Frameworks Supported by Rigid Octadentate Carboxylate Ligand: Synthesis, Structure Diversity, and Luminescence Properties
Author(s) -
Wu Dai,
Mo XiuFang,
He Piao,
Li HaiRu,
Yi XiaoYi,
Liu Chao
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100099
Subject(s) - carboxylate , uranyl , ligand (biochemistry) , luminescence , imidazole , crystallography , materials science , polyoxometalate , stereochemistry , chemistry , uranium , organic chemistry , metallurgy , catalysis , biochemistry , receptor , optoelectronics
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(3,5‐dicarboxyphenyl)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 co‐ligands. 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 − 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.