Polycatenation-driven self-assembly of nanoporous frameworks based on a 1D ribbon of rings: Regular structural evolution, interpenetration transformation, and photochemical modification

A series of nanoporous frameworks constructed by a polycatenated isoreticular 1Da ribbon of rings have been developed. The orientation of catenated ribbons can be fine tuned by varying counter anions, which allows both pore size and shape to be systematically adjusted in a pre-synthetic process. Distinct from conventional pore construction modes in which the organic linkers are alternately connected by metal nodes into a 3D periodic arrangement, the present polycatenation approach represents an alternative for constructing soft porous materials with tunable pore metrics and functions. Furthermore, these porous structures can interconvert into each other based on an anion-exchange process, accompanied by the transformation of the interpenetrating structures in different dimensional networks, which is unusual in porous frameworks. In addition, such a porous framework can be post-synthetically modified by a photoinduced [2+2] cycloaddition reaction, which not only achieves the surface modification (from conjugated to non-conjugated inner surface), but also triggers the structural transformation from low dimension to high dimension. Such a post-modification process reinforces the pore architecture through a covalent locking effect and has a great impact on the adsorption properties. Polycatenation approach: A unique example of polycatenation-driven assembly of porous frameworks with fine-tuning pore metrics as well as the structural transformation between the interpenetrated frameworks has been developed. Furthermore, the introduction of photochemical modification has made a great impact on the porous structure as well as the adsorption performance.