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A 1,8-naphthalenecarboxylic anhydride-4,5-dicarboxylate (L) bridged copper(II) dimeric molecular module [Cu2L2(DMF)2(H2O)2] (1) can self-organize into a solid-state supramolecular architecture. The combination of the multitopic contact sites of hydrogen bonds coupled with two bulky aromatic cores promoted the molecule to self-link into a solid-state supramolecular architecture, which was almost insoluble in water and common organic solvents. Solid 1 can heterogeneously catalyze the cross-coupling of arylboronic acids with imidazole in the absence of a base or additive to generate the corresponding coupling products in excellent yields in methanol at 50 °C, which can be recovered and recycled by a simple filtration and was used for six consecutive cycles with consistent activity.

Two new organic building units that contain dicarboxylate sites for their self-assembly with paddle- wheel (Cu2A2)4) units have been suc- cessfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo top- ologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST- 1. Because the organic linkers in ZJU- 35 and ZJU-36 are systematically en- larged, the pores in these two new porous MOFs vary from 10.8 � in HKUST-1 to 14.4 � in ZJU-35 and 16.5 � in ZJU-36, thus leading to their higher porosities with Brunauer- Emmett-Teller (BET) surface areas of 2899 and 4014 m 2 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 prelimi- narily 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 hexacarboxy- lates that contain m-benzenedicarboxy- late units with the (Cu2A2)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 (Cu2A2)4) units has provided great promise for the exploration of a large number of new tetra- and hexacarboxy- late organic linkers based on these new organic building units in which differ- ent 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.

Four porous metalloporphyrinic framework materials, [(CH3)2NH2][Zn2(HCOO)2(Mn(III)-TCPP)]·5DMF·2H2O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)2NH2][Cd2(HCOO)2(Mn(III)-TCPP)]·5DMF·3H2O (2), [Zn2(HCOO)(Fe(III)(H2O)-TCPP)]·3DMF·H2O (3), and [Cd3(H2O)6(μ2-O)(Fe(III)-HTCPP)2]·5DMF (4) were synthesized by heating a mixture of M(III)Cl-H4TCPP (M = Mn and Fe) and M' (M' = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M'2(COO)4 paddle-wheel subunits bridged by M(III)-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M' cations in 1 and 2 and homogeneously joins M' cations in 3. The μ2-O bridged Fe(III)-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.

A new bifunctional aromatic azolium derivative is designed and synthesized, which is used to construct two MOF′s containing imidazolium moieties.

A new bifunctional N-heterocyclic carbene (NHC) precursor was used to construct two metal–organic frameworks, which can anchor palladium(II) sites by post-modification, presenting remarkable framework dependent catalytic activities.