A pair of highly porous chiral metal–organic frameworks (CMOFs 1 and 2) were constructed from [Cu2(carboxylate)4] secondary building units (SBUs) and chiral 3,3′,6,6′- or 4,4′,6,6′-tetra(benzoate) ligands derived from 1,1′-binaphthyl-2,2′-phosphoric acid. Both 1 and 2 were active catalysts for Friedel–Crafts reactions between indole and imines. Interestingly, the 1-catalyzed asymmetric reactions yielded the major enantiomers of the opposite chirality to those afforded by the corresponding homogeneous catalyst. Structural analyses and QM/MM calculations revealed that the flip of product handedness results from the chiral environment of CMOF-1 cavity, similar to enzymatic catalysis in which the product stereoselectivity is determined by the enzyme pocket.

Three phosphorescent Ir and Ru complexes containing dicarboxylate functional groups have been doped into the framework of Zr6O4(OH)4(bpdc)6 (UiO-67, bpdc = para-biphenyldicarboxylate) to yield stable metal–organic frameworks (MOFs 1–3) which are highly porous with BET surface areas of 2568, 2292, and 1277 m2 g−1, respectively. The 3MLCT phosphorescence of 1–3 can be effectively quenched by O2 to provide an efficient method for oxygen detection.

A pair of highly porous chiral metal–organic frameworks (CMOFs 1 and 2) were constructed from [Cu2(carboxylate)4] secondary building units (SBUs) and chiral 3,3′,6,6′- or 4,4′,6,6′-tetra(benzoate) ligands derived from 1,1′-binaphthyl-2,2′-phosphoric acid. Both 1 and 2 were active catalysts for Friedel–Crafts reactions between indole and imines. Interestingly, the 1-catalyzed asymmetric reactions yielded the major enantiomers of the opposite chirality to those afforded by the corresponding homogeneous catalyst. Structural analyses and QM/MM calculations revealed that the flip of product handedness results from the chiral environment of CMOF-1 cavity, similar to enzymatic catalysis in which the product stereoselectivity is determined by the enzyme pocket.

Three phosphorescent Ir and Ru complexes containing dicarboxylate functional groups have been doped into the framework of Zr6O4(OH)4(bpdc)6 (UiO-67, bpdc = para-biphenyldicarboxylate) to yield stable metal–organic frameworks (MOFs 1–3) which are highly porous with BET surface areas of 2568, 2292, and 1277 m2 g−1, respectively. The 3MLCT phosphorescence of 1–3 can be effectively quenched by O2 to provide an efficient method for oxygen detection.