The structural uniqueness of covalent organic frameworks (COFs) has brought these new materials great potential for advanced applications. One of the key aspects yet to be developed is how to improve the robustness of covalently linked reticular frameworks. In order to make the best use of π-conjugated structures, we develop herein a "killing two birds with one stone" strategy and construct a series of ultrastable benzoxazole-based COFs (denoted as LZU-190, LZU-191, and LZU-192) as metal-free photocatalysts. Benefiting from the formation of benzoxazole rings through reversible/irreversible cascade reactions, the synthesized COFs exhibit permanent stability in the presence of strong acid (9 M HCl), strong base (9 M NaOH), and sunlight. Meanwhile, reticulation of the benzoxazole moiety into the π-conjugated COF frameworks decreases the optical band gap and therefore increases the capability for visible-light absorption. As a result, the excellent photoactivity and unprecedented recyclability of LZU-190 (for at least 20 catalytic runs, each with a product yield of 99%) have been illustrated in the visible-light-driven oxidative hydroxylation of arylboronic acids to phenols. This contribution represents the first report on the photocatalytic application of benzoxazole-based structures, which not only sheds new light on the exploration of robust organophotocatalysts from small molecules to extended frameworks but also offers in-depth understanding of the structure-activity relationship toward practical applications of COF materials.

Covalent organic frameworks (COFs) represent a new type of crystalline porous materials that are covalently assembled from organic building blocks. Construction of functional COFs is, however, a difficult task because it has to meet simultaneously the requirements for crystallinity and functionality. We report herein a facile strategy for the direct construction of chiral-functionalized COFs from chiral building blocks. The key design is to use the rigid scaffold 4,4'-(1H-benzo[d]imidazole-4,7-diyl)dianiline (2) for attaching a variety of chiral moieties. As a first example, the chiral pyrrolidine-embedded building block (S)-4,4'-(2-(pyrrolidin-2-yl)-1H-benzo[d]imidazole-4,7-diyl)dianiline (3) was accordingly synthesized and applied for the successful construction of two chiral COFs, LZU-72 and LZU-76. Our experimental results further showed that these chiral COFs are structurally robust and highly active as heterogeneous organocatalysts.

Droplet deposition on superhydrophobic surfaces has been a great challenge owing to the shortness of the impact contact time. Despite recent research progress regarding flat superhydrophobic surfaces, improving deposition on ubiquitous wired and curved superhydrophobic leaves remains challenging as their surface structures promote asymmetric impacts, thereby shortening the contact times and increasing the likelihood of droplet splitting. Here, we propose a strategy to solve the deposition problems based on an analysis of the impact dynamics and a rational selection of additives. Combining the prominent extension property of flexible polymers with surface tension reduction of the surfactant, the well-chosen binary additives cooperatively solve retention and coverage problems by limiting the fragment and enhancing local pinning and wetting processes at a very low usage. This work advances the understanding of droplet deposition by rationally selecting additives based on the impact dynamics, which is believed to be useful in a variety of spraying, coating, and printing applications.

“Bottom-up” embedding of thiophene derivatives into CMPs for highly efficient heterogeneous photocatalysis is reported.

Constructing s-tetrazine-embedded HCP photocatalysts for the green synthesis of benzimidazoles.