3D Porphyrin-Based Covalent Organic Frameworks

The design and synthesis of three-dimensional covalent organic frameworks (3D COFs) bearing photoelectric units have been considered as a big challenge. Herein, for the first time, we reported the targeted synthesis of two 3D porphyrin-based COFs (3D-Por-COF and 3D-CuPor-COF), starting from tetrahedral (3D-<i>T</i>_d) and square (2D-<i>C</i>₄) building blocks connected through [4 + 4] imine condensation reactions. On the basis of structural characterizations, 3D-Por-COF and 3D-CuPor-COF are microporous materials with high surface areas, and are proposed to adopt a 2-fold interpenetrated <b>pts</b> topology with <i>Pmc</i>2₁ space group. Interestingly, both 3D COFs are photosensitive and can be used as heterogeneous catalyst for generating singlet oxygen under photoirradiation. However, 3D-Por-COF shows enhanced photocatalytic activity compared with 3D-CuPor-COF, indicating the properties of 3D porphyrin-based COFs can be tuned by metalation of porphyrin rings. The results reported here will greatly inspire us to design and synthesize 3D COFs bearing other metalloporphyrins for interesting applications (e.g., catalysis) in the future

Engineering a Zirconium MOF through Tandem “Click” Reactions: A General Strategy for Quantitative Loading of Bifunctional Groups on the Pore Surface

Metal–organic frameworks (MOFs) assembled from linkers of identical length but with different functional groups have gained increasing interests recently. However, it is very challenging for precise control of the ratios of different functionalities. Herein, we reported a stable azide- and alkyne-appended Zr-MOF that can undergo quantitative tandem click reactions on the different functional sites, thus providing a unique platform for quantitative loading of bifunctional moieties. As an added advantage, the same MOF product can be obtained via two independent routes. The method is versatile and can tolerate a wide variety of functional groups, and furthermore, a heterogeneous acid–base MOF organocatalyst was synthesized by tandemly introducing both acidic and basic groups onto the predesigned pore surface. The presented strategy provides a general way toward the construction of bifunctional MOFs with a precise control of ratio of different functionalities for desirable applications in future