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In this work, nine new rare-earth metal-organic frameworks (RE-MOFs, where RE=Lu(III), Yb(III), Tm(III), Er(III), Ho(III), Dy(III), Tb(III), Gd(III), and Eu(III)) isostructural to Zr-MOF-808 are synthesized, characterized, and studied regarding their photophysical properties. Materials with high crystallinity and surface area are obtained from a reproducible synthetic procedure that involves the use of two fluorinated modulators. At the same time, these new RE-MOFs display tunable photoluminescent properties due to efficient linker-to-metal energy transfer promoted by the antenna effect, resulting in a series of RE-MOFs displaying lanthanoid-based emissions spanning the visible and near-infrared regions of the electromagnetic spectrum., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Ordered materials with predictable structures and properties can be made by a modular approach, using molecules designed to interact with neighbors and hold them in predetermined positions. Incorporating 4,6-diamino-1,3,5-triazin-2-yl (DAT) groups in modules is an effective way to direct assembly because each DAT group can form multiple N-H⋅⋅⋅N hydrogen bonds according to established patterns. We have found that modules with high densities of N(DAT) 2 groups can be made by base-induced double triazinylations of readily available amines. The resulting modules can form structures held together by remarkably large numbers of hydrogen bonds per molecule. Even simple modules with only 1-3 N(DAT) 2 groups and fewer than 70 non-hydrogen atoms can crystallize to form highly open networks in which each molecule engages in over 20 N-H⋅⋅⋅N hydrogen bonds, and more than 70 % of the volume is available for accommodating guests. In favorable cases, guests can be removed to create rigorously porous crystalline solids analogous to zeolites and metal-organic frameworks., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr 6 -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Owing to their high surface area, periodic distribution of metal sites, and water stability, zirconium-based metal-organic frameworks (Zr 6 -MOFs) have shown promising activity for the hydrolysis of nerve agents GD and VX, as well as the simulant, dimethyl 4-nitrophenylphosphate (DMNP), in buffered solutions. A hurdle to using MOFs for this application is the current need for a buffer solution. Here the destruction of the simulant DMNP, as well as the chemical warfare agents (GD and VX) through hydrolysis using a MOF catalyst mixed with a non-volatile, water-insoluble, heterogeneous buffer is reported. The hydrolysis of the simulant and nerve agents in the presence of the heterogeneous buffer was fast and effective., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)