A microporous Pb(II) metal-organic framework (MOF) [PbL(2)]·2DMF·6H(2)O (1) has been assembled from a N-oxide and amide doubly functionalized ligand HL (= N-(4-carboxyphenyl)isonicotinamide 1-oxide). Complex 1 features a three-dimensional (3D) framework possessing one-dimensional (1D) rhombic channels with dimensions of 13 × 13 Å(2). The 3D framework is built up from 1D PbO(2) chains that link ligands in parallel fashion to construct single-wall channels. When recrystallizing 1 in a DMSO-DMF mixture (3 : 5 v/v), a new coordination polymer, [PbL(2)]·DMF·2H(2)O (2), was obtained. Complex 2 is also a 3D framework containing 1D rectangular channels, but the channel dimensions become reduced in size to 13 × 8 Å(2) due to reorganization of the Pb(ii) coordination environment. The PbO(2) chains in 2 are reformed to link ligands in a double-wall fashion, significantly reducing the channel size. Even though, the guest exchange study indicates that the DMF molecules in 2 could be replaced with benzene molecules when immersing in benzene solvent, showing single-crystal-to-single-crystal (SC-SC) guest exchange in the solid state and leading to a daughter crystal [PbL(2)]·0.5C(6)H(6)·2H(2)O (2'). Desolvated 1 and 2 display preferential adsorption behaviors of water vapour over CO(2) due to the hydrophilic nature of the channels and the strong host-guest interactions. Catalytic tests indicate that desolvated 1 and 2 have size-selective catalytic activity towards the Knoevenagel condensation reaction.

The intermolecular catalysis toward the oxidation of hydrocarbons has been studied with a series of nanoscale coordination cages [CuI 4L4]4+, which are characteristic of the inherent catalytic activity by installing multiple Cu+ redox active ions on the cage vertices. The catalytic reactions take place out-cage on the surface active Cu+ sites, while the catalytic activity can be modulated in-cage by the guest anions, establishing an unprecedented host–guest regulable catalysis structural model for coordination cages in the sense of supramolecular catalysis. The catalytic behavior and mechanism, reactivity-structure relationship, and recyclable use of the cage catalysts have been thoroughly explored, in an effort to find the way to achieving robust catalysis through careful tuning of the solution stability and redox activity of cage structures by changing size and shape of guest anions.