The probing of volatile organic compounds (VOCs) is critical and challenging in biotechnology and environmental monitoring. Incorporation of luminescent moieties into metal–organic frameworks (MOFs) has produced many unique luminescent sensors for probing different VOCs. The emissions of most MOF sensors are based mainly on the single transitions of luminescent moieties, so the luminescence readouts are only predominant for some special VOCs. We use a natural amino acid derivative as the luminescent moiety to result in a lamellar coordination polymer, and further embed luminescent dye molecules in the crystal matrix to result in a luminescent dye@MOF sensor. The composite sensor exhibits excellent sensitivity for decoding different VOCs with clearly differentiable fluorescence emission by tuning the energy transfer efficiency from the organic ligand to the dye moieties. The composite luminescent sensor is self-calibrated, and much more stable and instantaneous than other more widely explored luminescent sensors.

Two metalloporphyrin octacarboxylates were used to link copper(II) nodes for the formation of two novel porous mixed-metal metal–organic frameworks (M′MOFs) containing nanopore cages (2.1 nm in diameter) or nanotubular channels (1.5 nm in diameter). The highly active Cu²⁺ sites on the nanotubular surfaces of the stable porous M′MOF ZJU-22, stabilized by three-connected nets, lead to the superior catalytic activity for the cross-dehydrogenative coupling (CDC) reaction.

Self-assembly of luminescent moieties into porous metal–organic frameworks (MOFs) has generated many luminescent platforms for probing volatile organic molecules (VOMs). However, most of those explored thus far have only been based on the luminescence intensity of one transition, which is not efficient for probing different VOMs. We have synthesized a luminescent MOF material containing 1D nanotube channels, and further developed a luminescent dye@MOF platform to realize the probing of different VOMs by tuning the energy transfer efficiency between two different emissions. The dye@MOF platform exhibits excellent fingerprint correlation between the VOM and the emission peak-height ratio of ligand to dye moieties. The dye@MOF sensor is self-calibrating, stable, and instantaneous, thus the approach should be a very promising strategy to develop luminescent materials with unprecedented practical applications.

Self-assembly of luminescent moieties into porous metal–organic frameworks (MOFs) has generated many luminescent platforms for probing volatile organic molecules (VOMs). However, most of those explored thus far have only been based on the luminescence intensity of one transition, which is not efficient for probing different VOMs. We have synthesized a luminescent MOF material containing 1D nanotube channels, and further developed a luminescent dye@MOF platform to realize the probing of different VOMs by tuning the energy transfer efficiency between two different emissions. The dye@MOF platform exhibits excellent fingerprint correlation between the VOM and the emission peak-height ratio of ligand to dye moieties. The dye@MOF sensor is self-calibrating, stable, and instantaneous, thus the approach should be a very promising strategy to develop luminescent materials with unprecedented practical applications.

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal–organic framework (M′MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M′MOF of [Zn₂(MnOH–TCPP)(DPNI)]⋅0.5 DMF⋅EtOH⋅5.5 H₂O (CZJ-1; CZJ=Chemistry Department of Zhejiang University; TCPP=tetrakis(4-carboxyphenyl)porphyrin); DPNI=N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has the type of doubly interpenetrated cubic α-Po topology in which the basic Zn₂(COO)₄ paddle-wheel clusters are bridged by metalloporphyrin to form two-dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three-dimensional porous structure. The porosity of CZJ-1 has been established by both crystallographic studies and gas-sorption isotherms. CZJ-1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94 % to the mixture of cyclohexanone (K) and cyclohexanol (A) (so-called K–A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M′MOF catalyst.

Two new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu₂(CO₂)₄] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST-1. Because the organic linkers in ZJU-35 and ZJU-36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST-1 to 14.4 Å in ZJU-35 and 16.5 Å in ZJU-36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m² g⁻¹ for ZJU-35 and ZJU-36, respectively. High-pressure gas-sorption isotherms indicate that both ZJU-35 and ZJU-36 can take up large amounts of CH₄ and CO₂, and are among the few porous MOFs with the highest volumetric storage of CH₄ under 60 bar and CO₂ under 30 bar at room temperature. Their potential for high-pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU-35 and ZJU-36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH₄ under 60 bar and CO₂ under 30 bar at room temperature are those self-assembled from organic tetra- and hexacarboxylates that contain m-benzenedicarboxylate units with the [Cu₂(CO₂)₄] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self-assembly with [Cu₂(CO₂)₄] units has provided great promise for the exploration of a large number of new tetra- and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.