A porous Zr-MOFs (JLU-MOF50) with exceptional stabilities has been synthesized. As a dual functional material, JLU-MOF50 displays not only a high trapping capacity and an adsorption rate, but also effective detecting performance for Cr2O72− in the aqueous phase.

Owing to the finite building blocks and difficulty in structural identification, it remains a tremendous challenge to elaborately design and synthesize three‐dimensional covalent organic frameworks (3D COFs) with predetermined topologies. Herein, we report the first two cases of 3D COFs with the non‐interpenetrated hea net, termed JUC‐596 and JUC‐597, by using the combination of tetrahedral and triangular prism building units. Due to the presence of triptycene functional groups and fluorine atoms, JUC‐596 exhibits an exceptional performance in the H2 adsorption up to 305 cm3 g−1 (or 2.72 wt%) at 77 K and 1 bar, which is higher than previous benchmarks from porous organic materials reported so far. Furthermore, the strong interaction between H2 and COF materials is verified through the DFT theoretical calculations. This work represents a captivating example of rational design of functional COFs based on a reticular chemistry guide and demonstrates its promising application in clean energy storage.

By using the mixed-linker strategy, a new pillar-layered luminescence Zn-LMOF (JLU-MOF71) ([Zn2­Na2­(TPHC)­(4,4-Bipy)­(DMF)]·​8H2O) (TPHC = [1,1′:​2′,1″-ter­phen­yl]-3,­3″,­4,­4′,­4″,5′-hexa­car­boxylic acid, 4,4-bipy = 4,4-bipyr­i­dine, DMF = N,N-dimethyl­formamide) was successfully synthesized and structurally characterized. JLU-MOF71 is constructed by the 4,4-bipy pillars and 2D layers which consist of Zn2+ and TPHC ligands, and displays a rare fsh topology. Benefiting from the uncoordinated carboxylate sites in the framework, JLU-MOF71 not only can sensitively detect trace amounts of individual Fe3+ and 2,4,6-trinitrophenol (TNP) through luminescence quenching but also exhibits high selectivity when other competing analytes exist. Besides, TNP can also be effectively monitored with the help of the shifting direction of luminescent spectra (red shift) which has rarely been reported before. On the basis of the aforementioned, JLU-MOF71 can be considered as a potential luminescence sensor for detecting Fe3+ and TNP.

heterogeneous catalysis, [4] and others. [5] At present, most of the discovered COFs are still 2D frameworks with eclipsed stacking structures because of their simpler synthesis and easier functionalization. Compared with 2D analogues, 3D functionalized COFs have recently attracted more and more attention due to their unique pore structures and higher specific surface areas. [6] For example, we have acquired a series of 3D functionalized COFs, [7] for example, 3D tetrathiafulvalene-based COFs for tunable electrical conductivity, 3D carboxy-functionalized COF for selective ion adsorption, and 3D Salphen-based COFs as catalytic antioxidants. Despite the aforementioned efforts in the in-situ synthesis and post-synthesis modifications, the functionalization of 3D COFs still remains largely undeveloped up to now, especially 3D architectures with stimuli-responsive functions, [8] due to the lacking of building units, the difficulty of directional synthesis, and the sophisticated procedure for introducing functional groups into the framework.It is well-known that hydrazone and its derivatives are significant synthons for numerous transformations, and their CN groups can undergo efficiently reversible structures betweenThe property expansion of 3D functionalized covalent organic frameworks (COFs) is important for developing their potential applications. Herein, the first case of 3D hydrazone-decorated COFs as pH-triggered molecular switches is reported, and their application in the stimuli-responsive drug delivery system is explored. These functionalized COFs with hydrazone groups on the channel walls are obtained via a multi-component bottom-up synthesis strategy. They exhibit a reversible E/Z isomerization at various pH values, confirmed by UV-vis absorption spectroscopy and proton conduction. Remarkably, after loading cytarabine (Ara-C) as a model drug molecule, these pH-responsive COFs show an excellent and intelligent sustained-release effect with an almost fourfold increase in the Ara-C release at pH = 4.8 than at pH = 7.4, which will effectively improve drug-targeting. Thus, these results open a way toward designing 3D stimuli-responsive functionalized COF materials and promote their potential application as drug carriers in the field of disease treatment.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202102630.