Merissa N. Morey, Christine M. Montone, Michael R. Dworzak, Glenn P. A. Yap and Eric D. Bloch
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引用次数: 0
摘要
人们对锆基多孔配位笼进行了广泛的研究,结果表明,由于锆基多孔配位笼的可调性和稳定性,它们在许多应用领域都具有潜在的用途,这可能是由于锆基多孔配位笼在分子上相当于 UiO-66 (Zr6(μ3-O)4(μ2-OH)4(C8O4H4)6)的 8 Å 小四面体孔隙。附着在这些分子材料上的官能团赋予了它们一系列可调的特性。所谓多变量 MOF,即在一个结构中的不同桥接配体上含有多种类型的官能团,这种结构很常见,但在永久性微孔分子材料中加入多种官能团却具有挑战性。通过将混合配体(或称异配体)合成策略应用于笼状结构的形成,我们设计出了一种简单易行的一锅合成法,在篮状(或称 Zr12L6)几何结构中合成了 10 Å 锆基分子笼,其中包含 11 种不同配体中 3:3 比例的两种功能基团组合。此外,我们还使用了立体受阻的配体,如 5-苄氧基苯二甲酸酯,结果表明配体的几何形状决定了笼子的几何形状。通过这种方法,可以在分子笼中加入多种功能基团,而且可以轻松控制加入的分子比例。有了这一策略,我们发现,一直难以合成锆笼子的配体,如 2,5-二羟基苯二甲酸酯,现在也能成功地结合到多孔结构中。
Tunable synthesis of heteroleptic zirconium-based porous coordination cages†
Zirconium-based porous coordination cages have been widely studied and have shown to be potentially useful for many applications as a result of their tunability and stability, likely as a result of their status as a molecular equivalent to the small 8 Å tetrahedral pores of UiO-66 (Zr6(μ3-O)4(μ2-OH)4(C8O4H4)6). Functional groups attached to these molecular materials endow them with a range of tunable properties. While so-called multivariate MOFs containing multiple types of functional groups on different bridging ligands within a structure are common, incorporating multiple functional moieties in permanently microporous molecular materials has proved challenging. By applying a mixed-ligand, or heteroleptic, synthesis strategy to cage formation, we have designed a straight-forward, one-pot synthesis of 10 Å zirconium-based molecular cages in a basket-shaped, or Zr12L6, geometry containing 3 : 3 ratios of combinations of two types of functional moieties from 11 different ligand options. Additionally, using more sterically hindered ligands, such as 5-benzyloxybenzene dicarboxylate, we show that ligand size governs the resulting cage geometry. This method allows for multiple functional groups to be incorporated in molecular cages and the ratio of moieties incorporated can be easily controlled. With this strategy in hand, we show that ligands for which zirconium cage syntheses have been elusive, such as 2,5-dihydroxybenzene dicarboxylate, have now been successfully incorporated into porous structures.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.