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Achieving enhanced or blue‐shifted emission from piezochromic materials remains a major challenge. Covalent organic frameworks (COFs) are promising candidates for the development of piezochromic materials owing to their dynamic structures and adjustable optical properties, where the emission behaviors are not solely determined by the functional groups, but are also greatly influenced by the specific geometric arrangement. Nevertheless, this area remains relatively understudied. In this study, a successful synthesis of a series of bicarbazole‐based COFs with varying topologies, dimensions, and linkages was conducted, followed by an investigation of their structural and emission properties under hydrostatic pressure generated by a diamond anvil cell. Consequently, these COFs exhibited distinct piezochromic behaviors, particularly a remarkable pressure‐induced emission enhancement (PIEE) phenomenon with a 16‐fold increase in fluorescence intensity from three‐dimensional COFs, surpassing the performance of CPMs and most organic small molecules with PIEE behavior. On the contrary, three two‐dimensional COFs with flexible structures exhibited rare blue‐shifted emission, whereas the variants with rigid and conjugated structures showed common red‐shifted and reduced emission. Mechanism research further revealed that these different piezochromic behaviors were primarily determined by interlayer distance and interaction. This study represents the first systematic exploration of the structures and emission properties of COFs through pressure‐treated engineering and provides a new perspective on the design of piezochromic materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Three‐dimensional (3D) covalent organic frameworks (COFs) are crystalline porous polymers with potential in numerous high‐tech applications, but the linkages involved in their synthesis are still rather limited. Herein, we report novel 3D sp2 carbon‐linked COFs fabricated by the formation reaction of C=C bonds and their application in fluorescence imaging. These new COFs, namely JUC‐580 and JUC‐581, show high stability and excellent light‐emitting properties in solid state and dispersed in various solvents. Furthermore, we investigate the potential application of JUC‐581 as a drug carrier combined with fluorescence imaging. These results indicate that 3D sp2 carbon‐linked COFs are not only potential drug‐loaded and sustained release materials but also promising cell fluorescent stains. This study thus expands the structural categories of 3D COFs based on different linkages, and promotes their prospective applications for biomedicine and fluorescent materials. [ABSTRACT FROM AUTHOR]

Piezochromic materials with pressure-dependent photoluminescence tuning properties are important in many fields, such as mechanical sensors, security papers, and storage devices. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials (CPMs) with structural dynamics and tunable photophysical properties, are suitable for designing piezochromic materials, but there are few related studies. Herein, we report two dynamic three-dimensional COFs based on aggregation-induced emission (AIE) or aggregation-caused quenching (ACQ) chromophores, termed JUC-635 and JUC-636 (JUC=Jilin University China), and for the first time, study their piezochromic behavior by diamond anvil cell technique. Due to the various luminescent groups, JUC-635 has completely different solvatochromism and molecular aggregation behavior in the solvents. More importantly, JUC-635 with AIE effect exhibits a sustained fluorescence upon pressure increase (≈3 GPa), and reversible sensitivity with high-contrast emission differences (Δλ em =187 nm) up to 12 GPa, superior to other CPMs reported so far. Therefore, this study will open a new gate to expand the potential applications of COFs as exceptional piezochromic materials in pressure sensing, barcoding, and signal switching., (© 2023 Wiley-VCH GmbH.)

The development of novel zeolite-like materials with large channel windows and high stability is of importance but remains a tremendous challenge. Herein, we report the first example of a 3D covalent organic framework with zeolitic network, namely the zeolitic organic framework (ZOF). By combining two kinds of tetrahedral building blocks with fixed or relatively free bond angles, ZOF-1 with the zeolitic crb net has been successfully synthesized. Its structure was determined by the single-crystal 3D electron diffraction technique. Remarkably, ZOF-1 shows high chemical stability, large pore size (up to 16 Å), and excellent specific surface area (≈2785 m 2  g -1 ), which is superior to its analogues with the same network, including traditional aluminosilicate zeolites and zeolitic imidazole frameworks. This study thus opens a new avenue to construct zeolite-like materials with pure organic frameworks and will promote their potential applications in adsorption and catalysis for macromolecules., (© 2022 Wiley-VCH GmbH.)