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Synthesis, Structures, and Properties of Uranyl Hybrids Constructed by a Variety of Mono- and Polycarboxylic Acids
journal contribution
posted on 2013-11-04, 00:00 authored by Weiting Yang, Song Dang, Hao Wang, Tao Tian, Qing-Jiang Pan, Zhong-Ming SunA series of uranyl–organic
coordination polymers have been
hydrothermally synthesized by using a variety of carboxylic ligands,
3,3′-((2-((3-carboxyphenoxy)methyl)-2-methylpropane-1,3-diyl)bis(oxy))dibenzoic
acid (H3L1), 4,4′-(3-(4-carboxyphenethyl)-3-hydroxypentane-1,5-diyl)dibenzoic
acid (H3L2), chelidamic acid (H2L3), and benzoic acid (HL4) in the presence of N-bearing
coligands, including 2,2′-bipyridine (bipy), 1,10-phenanthroline
(phen), 1-([1,1′-biphenyl]-4-yl)-1H-imidazole
(bpi), and 1,4-di(1H-imidazol-1-yl)benzene (dib).
Compounds (UO2)(HL1) (1) and Zn(H2O)3(UO2)2(O)(OH)(L2)·H2O (2) are constructed by semirigid
ligands. The former is a one-dimensional ribbon-like structure with
UO7 pentagonal bipyramids as the building unit, while the
latter adopts a tetramer of UO7 pentagonal bipyramids to
build a layered structure. Mononuclear UO7 pentagonal bipyramids
are connected by L3 groups to generate a two-dimensional
arrangement of UO2(L3)(H2dib)0.5 (3), in which the protonated dib molecules
provide space filling and form π···π interactions
with the layers. Compounds UO2(L3)(phen) (4), UO2(L3)2(Hbpi)2 (5), and UO2(L4)2(bipy)
(6) are molecular complexes, in which 4 and 6 are neutral, and 5 comprises protonated bpi
as the counterion. The uranyl center in compound 4 is
chelated by one phen and one L3 group to form a UO5N2 pentagonal bipyramid, while in compound 5, two L3 groups are coordinated to an uranyl center,
producing a UO8 polyhedron. Compound 6 consists
of a UO6N2 polyhedron of uranyl unit coordinated
by one bipy and two benzoate groups. Compounds Zn(phen)3[(UO2)(C2O4)(L4)]2 (7) and Zn(bpi)2(UO2)(O)(C2O4)0.5(L4)·H2O (8) feature one-dimensional structures. In 7, UO7 pentagonal bipyramids are alternatively connected
by oxalate groups to form the chain, in which unidentate benzoate
groups are coordinated to the uranium atoms. Zn(phen)3 cations
fill the void space of the chains to compensate the negative charge.
Differently, the chain of 8 can be seen as the heterometallic
tetramer of UO7 and ZnO2N2 polyhedra
connected by oxalate groups, and then bpi and benzoate groups are
coordinated to the chain. All of the compounds have been characterized
by IR and photoluminescent spectroscopy, and compounds 2, 3, 5, 6, and 8 exhibit characteristic emissions of uranyl cations.
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Keywords
benzoate groupsZnO 2N polyhedraUO 5N pentagonal bipyramid2LL 3 groupHLUranyl Hybrids ConstructedUO 6N polyhedronIRunidentate benzoate groupsprotonated dib moleculesUO 7 pentagonal bipyramidsUO 8 polyhedronPolycarboxylic AcidsA seriesL 3 groupsH 3L chelidamic aciduranyl centerMononuclear UO 7 pentagonal bipyramidsoxalate groups
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