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A new porous metal–metalloporphyrin framework, MMPF-10, has been constructed from an octatopic porphyrin ligand, which links copper paddlewheel units to form a framework with fmj topology. In situ metallation of the porphyrin ligands provides MMPF-10 with two unique accessible Cu(II) centers. This allows it to behave as an efficient Lewis acid catalyst in the first reported reaction of CO2 with aziridines to synthesize oxazolidinones catalyzed by an MMPF.

We unveil a unique kinetic driven separation material for selectively removing linear paraffins from iso-paraffins via a molecular sieving mechanism. Subsequent carbonization and thermal treatment of CD-MOF-2, the cyclodextrin metal-organic framework, afforded a carbon molecular sieve with a uniform and reduced pore size of ca. 5.0 Å, and it exhibited highly selective kinetic separation of n-butane and n-pentane from iso-butane and iso-pentane, respectively.

In this work, we illustrate a template strategy to create extra pores in microporous carbon for enhancing ambient-pressure CO2 uptake, as exemplified in the context of carbonizing the silicon-containing POP, PPN-4, followed by removal of the silicon template. The resultant PPN-4/C600 demonstrates a remarkable enhancement of CO2 uptake capacity at 295 K and 1 bar by a factor of 2.3 compared to the parent PPN-4.

Two rht-type metal-organic frameworks (MOFs) based upon the tetrazolate moiety and pyrazolate moiety, respectively, have been investigated for carbon dioxide (CO2) adsorption and selective adsorption of CO2 over CH4, which shows that the rht-MOF featuring the pyrazolate moiety demonstrates superior performances compared to the rht-MOF based on the tetrazolate moiety. In spite of more exposed nitrogen atoms in the tetrazolate-based rht-MOF, the counter-intuitive observations of CO2 capture in the two rht-MOFs were interpreted by computational studies, which reveal that the local electric field favours more than the richness of exposed nitrogen atoms for the interactions with CO2 molecules.

The introduction of the combination of open metal site (OMS) and π-complexation into MOF has led to very high ethylene-ethane adsorption selectivity at 318 K, as illustrated in the context of MIL-101-Cr-SO3Ag. The interactions with ethylene from both OMS and π-complexation in MIL-101-Cr-SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest that π-complexation contributes dominantly to the high ethylene-ethane adsorption selectivity.

A series of prototypal metal-organic frameworks (MOFs) consisting of polyhedral cages with accessible Lewis-acid sites, have been systematically investigated for Friedländer annulation reaction, a straightforward approach to synthesizing quinoline and its derivatives. Amongst them MMCF-2 demonstrates significantly enhanced catalytic activity compared with the benchmark MOFs, HKUST-1 and MOF-505, as a result of a high-density of accessible Cu(II) Lewis acid sites and large window size in the cuboctahedral cage-based nanoreactor of MMCF-2.

Dual functionalization of porous aromatic frameworks (PAFs) has been illustrated in the context of incorporating two antagonistic sites of strong acid and strong base into the highly porous and highly robust PAF-1 via stepwise post-synthetic modification. The resulting bifunctionalized PAF-1 exhibits excellent performances in catalyzing a series of cascade reactions and demonstrates superior chemical stability compared to the counterparts of mesoporous silica and MOFs, thereby opening the door for dual functionalization of PAFs as a new platform for heterogeneous cascade catalysis.

Pre-introducing an extra carbon source into the porous aromatic framework of PAF-1 followed by thermolysis affords a new microporous carbon material, which demonstrates a CO2 uptake capacity of 93 cm(3) g(-1) (equivalent to 4.1 mmol g(-1) or 18.2 wt%) at 295 K and 1 bar.

A strategy for building highly connected robust MOFs from linear ligands is exemplified by the construction of MTAF-4, a rare (6,9)-connected MOF, based on the custom-designed bifunctional linear ligand, 4-(1,2,3-triazol-4-yl)-benzoate, that connects two types of highly connected zinc cluster moieties generated in situ. MTAF-4 is robust and permanently microporous and is capable of adsorbing CO2, H2 and CH4 under high pressures.

A highly porous porphyrin-based organic polymer, PCPF-1, was constructed via homo-coupling reaction of the custom-designed porphyrin ligand, 5,10,15,20-tetrakis(4-bromophenyl)porphyrin. PCPF-1 possesses a large BET surface area of over 1300 m(2) g(-1) (Langmuir surface area of over 2400 m(2) g(-1)) and exhibits strong hydrophobicity with a water contact angle of 135°, and these features afford it the highest adsorptive capacities for saturated hydrocarbons and gasoline among sorbent materials reported thus far, as well as render it the capability to remove oil from water.

Two homochiral organocatalytic MOMs were prepared using tetra- and octa-carboxylate ligands, respectively. The nanoscopic channels in these MOMs are lined by organonocatalytic chiral phosphoric acid derivatives of binol and ocMOM-1 exhibited improved enantioselectivity over the parent ligand in the context of transfer hydrogenation of a series of benzoxazines.

Cucurbit[7]uril (CB[7]), in its amorphous solid state, shows one of the highest CO(2) sorption capacities among known organic porous materials at 298 K and 0.1 and 1 bar. In addition to the highest CO(2) capacity, CB[7] also shows remarkable selectivity of CO(2) over N(2) and CH(4). These properties, along with the existence of readily available precursors, indicate amorphous CB[7] might find applications in recycling CO(2) particularly considering the easy synthesis and potentially low manufacturing costs.

Cavities up to 4 nm have been introduced into a hierarchically-assembled metal-organic framework by adopting an angular, semi-flexible tetratopic ligand. The resulting MOF possesses permanent porosity and exhibits stepwise sorption isotherms for O(2) and N(2) gases.