Employing a rational design strategy
to construct porous metal–organic frameworks (MOFs) with predictable
structures for specific applications still remains one of the most
compelling challenges. Here, a novel two-dimensional (2D) bilayer
(FJI-H16) based on Zn/Cd heterometal clusters has been
constructed throughout a heterometal strategy, further introducing
pillar ligands with different sizes and flexibilities that expand
such 2D bilayer structures into two novel three-dimensional (3D) frameworks
(FJI-H17, FJI-H18), in which both the pore
size and flexibility of the new-formed 3D frameworks can be tuned.
Further gas adsorption research indicates that the less porous FJI-H16 has the highest H2 adsorption, while the
very porous FJI-H17 has the highest CO2 adsorption.
The relationship between gas adsorption properties and pore characteristics
also has been investigated, which will provide a potential strategy
that can improve gas adsorption in designing porous MOFs.
Coordination self‐assemblies have attracted more and more attentions from chemists because of their beautiful structures and wide applications, and a number of excellent reviews that focus on either synthesis or application have been published. This paper will hightlight how to controllablly construct supramolecular assemblies based on flexibility of ligands driven by different external stimuli. Herein, not only various discrete metal‐organic aggregates including M2L2 type metallocycles, M2L4/M2L6/M3L2/M6L4/M6L8 type metallocages have been prepared, but also many well‐organized ensembles based on such new‐formed discrete aggretates have been further assembled driven by suitable external stimuli. Also, controllable self‐assembly processes accompanied with structure changes have been developed. It is expected that this paper will provide a potential strategy for developing novel coordination assemblies that can be comparable to biomacromolecules from organism.
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