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We present herein the first example of metal-organic frameworks postfunctionalized with peptides. Our microwave-assisted postsynthetic modification method yields enantiopure peptides anchored inside MOF cavities. Al-MIL-101-NH2, In-MIL-68-NH2, and Zr-UiO-66-NH2 were chosen as starting platforms. A single amino acid and various oligopeptides are grafted with yields up to 60% after a 30 min microwave-assisted coupling-deprotection sequence. This allows efficient preparation of a library of functional hybrid solids for molecular recognition applications such as sensing, separation, or asymmetric catalysis, as demonstrated here for the chiral aldol reaction. [ABSTRACT FROM AUTHOR]

The one-pot postfunctionalization allows anchoring a molecular nickel complex into a mesoporous metal-organic framework (Ni@(Fe)MIL-101). It is generating a very active and reusable catalyst for the liquid-phase ethylene dimerization to selectively form 1-butene. Higher selectivity for 1-butene is found using the Ni@(Fe)MIL-101 catalyst than reported for molecular nickel diimino complexes. [ABSTRACT FROM AUTHOR]

Hydrogen uptake at 298 K and 30 bar in hybrid sorbents consisting of n-hexane confined in MIL-101 is found to be 22 times larger than in sole n-hexane. The enhanced solubility in MIL-101, found to be 3 times larger than in mesoporous silica of similar pore size, highlights the key roles played by surface chemistry and accessible surface area. [ABSTRACT FROM AUTHOR]