Modulation of the assembly fashion among metal–organic frameworks for enantioretentive epoxide activationElectronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3nh00419h

Highly enantioretentive alcoholysis of epoxides is an important way to synthesize enantiopure β-alkoxy alcohols, which are irreplaceable intermediates demanded by biomedicines, fine chemicals and other industries. In this report, we exploit a series of Zr-based metal–organic frameworks (Zr-MOFs) as the catalysts to achieve high activity and enantioretentivity in the alcoholysis of styrene oxide viamodulating their assembly fashions. It is explored that hcp-UiO-66not only exhibits a ∼10 fold improved catalytic activity than both hxl-CAU-26and fcc-UiO-66of varied assemblies but also maintains superior product enantioretentivity. Theoretic calculations together with experimental proof discloses the origin of distinct catalytic activity caused by different assembly fashions. This assembly modulation strategy offers a potential protocol for seeking high-performance catalysts among MOFs by virtue of their rich polymorphisms.