Perl David, Lee Seok J, Ferguson Alan, Jameson Geoffrey B, Telfer Shane G
MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Natural Sciences, Massey University, Palmerston North, New Zealand.
Nat Chem. 2023 Oct;15(10):1358-1364. doi: 10.1038/s41557-023-01277-z. Epub 2023 Aug 3.
Interpenetrated metal-organic frameworks (MOFs) comprise two or more lattices that are mutually entangled. Interpenetration can be used to tune the structures and pore architectures of MOFs to influence, for example, their stability or interactions with guest molecules. The interpenetrating sublattices are typically identical, but hetero-interpenetrated MOFs, which consist of sublattices that are different from one another, have also been serendipitously produced. Here we describe a strategy for the deliberate synthesis of hetero-interpenetrated MOFs. We use the cubic α-MUF-9 framework as a host sublattice to template the growth of a second sublattice within its pores. Three different secondary sublattices are grown-two of which are not known as standalone MOFs-leading to three different hetero-interpenetrated MOFs. This strategy may serve to combine different properties into one material. We produce an asymmetric catalysis by allocating separate roles to the interpenetrating sublattices in a hetero-interpenetrated MOF: an achiral secondary amine on one sublattice provides the catalytic activity, while the chiral α-MUF-10 host imparts asymmetry to aldol and Henry reactions.
互穿金属有机框架（MOFs）由两个或更多相互缠结的晶格组成。互穿可用于调节MOFs的结构和孔结构，从而影响其稳定性或与客体分子的相互作用等。互穿的子晶格通常是相同的，但也偶然产生了由彼此不同的子晶格组成的异质互穿MOFs。在此，我们描述了一种有意合成异质互穿MOFs的策略。我们使用立方α-MUF-9框架作为主体子晶格，以在其孔内模板化第二个子晶格的生长。生长出三种不同的二级子晶格，其中两种并非独立的MOFs，从而得到三种不同的异质互穿MOFs。该策略可用于将不同性质结合到一种材料中。我们通过在异质互穿MOF中为互穿的子晶格分配不同角色来实现不对称催化：一个子晶格上的非手性仲胺提供催化活性，而手性α-MUF-10主体赋予羟醛反应和亨利反应不对称性。
