Seven three dimensional (3D) uranyl organic frameworks (UOFs), formulated as [NH
4][(UO
2)
3(HTTDS)(H
2O)] ( 1 ), [(UO
2)
4(HTTDS)
2](HIM)
6 ( 2 , IM=imidazole), [(UO
2)
4(TTDS)(H
2O)
2(Phen)
2] ( 3 , Phen=1,10-phenanthroline), [Zn(H
2O)
4]
0.5[(UO
2)
3(HTTDS)(H
2O)
4] ( 4 ), and {(UO
2)
2[Zn(H
2O)
3]
2(TTDS)} ( 5 ), {Zn(UO
2)
2(H
2O)(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
2O)
7](TTDS)
2} ( 7 ) have been hydrothermally prepared using a rigid octadentate carboxylate ligand, tetrakis(3,5-dicarboxyphenyl)silicon(H
8TTDS). 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
2CR)
4] cluster was found in the structure. It acts as an inorganic building unit together with the dimer [(UO
2)
2(O
2CR)
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.
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