Synthesis, structures, and properties of uranyl hybrids constructed by a variety of mono- and polycarboxylic acids.
Synthesis, structures, and properties of uranyl hybrids constructed by a variety of mono- and polycarboxylic acids.
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DOI：
10.1021/ic4012444
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发表时间：
2013-10
影响因子：
4.6
通讯作者：
Weiting Yang;Song Dang;Hao Wang;Tao Tian;Qingjiang Pan;Zhong‐Ming Sun
中科院分区：
文献类型：
--
作者：
Weiting Yang;Song Dang;Hao Wang;Tao Tian;Qingjiang Pan;Zhong‐Ming Sun
以3，3 '-三甲基吡啶为配体，水热法合成了一系列铀酰有机配位聚合物（（2-（（3-羧基苯氧基）甲基）-2-甲基丙烷-1，3-二基）双（氧基））二苯甲酸（H3 L（1）），4，4 '-（3-（4-羧基苯乙基）-3-羟基戊烷-1，5-二基）二苯甲酸（H3 L（2））、白屈菜氨酸（H2 L（3））和苯甲酸（HL（4）），2 ′-联吡啶（bipy）、1，10-菲咯啉（phen）、1-（[1，1 ′-联苯基]-4-基）-1H-咪唑（bpi）和1，4-二（1H-咪唑-1-基）苯（dib）。化合物（UO_2）（HL（1））（1）和Zn（H_2 O）_3（UO_2）_2（O）（OH）（L（2））·H_2 O（2）由半刚性配体构成。前者是以UO 7五角双锥为构筑单元的一维带状结构，而后者是以UO 7五角双锥的四聚体为构筑单元的层状结构。单U O 7五角双锥通过L（3）基团连接，形成U O 2（L（3））（H2 dib）0.5（3）的二维排列，其中质子化的dib分子提供空间填充并与层形成π···π相互作用。化合物UO 2（L（3））（phen）（4）、UO 2（L（3））2（Hbpi）2（5）和UO 2（L（4））2（bipy）（6）是分子配合物，其中4和6是中性的，5包含质子化的bpi作为反离子。化合物4中的铀酰中心被一个phen和一个L（3）基团螯合形成UO_5 N_2五角双锥，而在化合物5中，两个L（3）基团与铀酰中心配位，形成UO_8多面体。化合物6由铀酰单元的UO_6 N_2多面体与一个联吡啶和两个苯甲酸酯基团配位组成。化合物Zn（phen）3[（UO 2）（C2 O 4）（L（4））]2（7）和Zn（bpi）2（UO 2）（O）（C2 O 4）0.5（L（4））·H2O（8）具有一维结构。在7中，UO 7五角双锥通过草酸根基团交替连接形成链，其中单齿苯甲酸根基团与铀原子配位。Zn（phen）3阳离子填充链的空隙空间以补偿负电荷。8的链可以看作是由草酸根连接的UO_7和ZnO_2N_2多面体的异金属四聚体，然后bpi和苯甲酸根配位到链上。所有的化合物已通过IR和光致发光光谱进行了表征，化合物2，3，5，6，和8表现出铀酰阳离子的特征发射。
A 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 (H3L(1)), 4,4'-(3-(4-carboxyphenethyl)-3-hydroxypentane-1,5-diyl)dibenzoic acid (H3L(2)), chelidamic acid (H2L(3)), and benzoic acid (HL(4)) 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)(HL(1)) (1) and Zn(H2O)3(UO2)2(O)(OH)(L(2))·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 L(3) groups to generate a two-dimensional arrangement of UO2(L(3))(H2dib)0.5 (3), in which the protonated dib molecules provide space filling and form π···π interactions with the layers. Compounds UO2(L(3))(phen) (4), UO2(L(3))2(Hbpi)2 (5), and UO2(L(4))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 L(3) group to form a UO5N2 pentagonal bipyramid, while in compound 5, two L(3) 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)(L(4))]2 (7) and Zn(bpi)2(UO2)(O)(C2O4)0.5(L(4))·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.