The photoinduced regio- and enantioselective coupling of naphthols and derivatives thereof is achieved in the confined chiral coordination space of a Ru metalloligand based cage. The racemic or enantiopure cages encapsulate naphthol guests, which then undergo a regiospecific 1,4-coupling, rather than the normal 1,1-coupling, to form 4-(2-hydroxy-1-naphthyl)-1,2-napthoquinones; moderate stereochemical control is achieved with homochiral cages. The photoreactions proceed under both aerobic and anaerobic conditions but through distinct pathways that nevertheless involve the same radical intermediates. This unusual dimerization constitutes a very rare example of asymmetric induction in biaryl coupling by making use of coordination cages with dual functionality-photoredox reactivity and stereoselectivity.

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Porous porphyrin metal-organic frameworks (PMOFs) provide promising platforms for studying CO capture and conversion (C3) owing to their versatility in photoelectric, catalytic, and redox activities and porphyrin coordination chemistry. Herein, we report the C3 application of two PMOFs by engineering the coordination space through the introduction of two catalytic metalloporphyrins doped with rhodium or iridium, Rh-PMOF-1 and Ir-PMOF-1, both of which can serve as heterogeneous catalysts for the chemical fixation of CO into cyclic carbonates with yields of up to 99 %. Remarkably, the catalytic reactions can effectively proceed under low CO concentrations and high yields of 83 % and 73 % can be obtained under 5 % CO in the presence of Rh-PMOF-1 and Ir-PMOF-1, respectively. The synergistic effect of the metalloporphyrin ligand and the Zr O cluster, in combination with the CO concentration effect from the pore space, might account for the excellent catalytic performance of Rh-PMOF-1 under low CO concentration. Recycling tests of Rh-PMOF-1 show negligible loss of catalytic activity after 10 runs.

Inherently chiral calixarenes, whose chirality is based on the absence of a planar symmetry or an inversion center in the molecules as a whole through the asymmetric array of several achiral groups upon the three-dimensional calix-skeletons, are challenging and attractive chiral molecules, because of their potential in supramolecular chemistry. The synthesis and optical resolution of all varieties of inherently chiral calixarenes are systematically discussed and classified, and their applications in chiral recognition and asymmetric catalysis are thoroughly illustrated in this review.

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Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

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