Long Time CO 2 Storage Under Ambient Conditions in Isolated Voids of a Porous Coordination Network Facilitated by the "Magic Door" Mechanism.

A coordination network containing isolated pores without interconnecting channels is prepared from a tetrahedral ligand and copper(I) iodide. Despite the lack of accessibility, CO 2 is selectively adsorbed into these pores at 298 K and then retained for more than one week while exposed to the atmosphere. The CO 2 adsorption energy and diffusion mechanism throughout the network are simulated using Matlantis, which helps to rationalize the experimental results. CO 2 enters the isolated voids through transient channels, termed "magic doors", which can momentarily appear within the structure. Once inside the voids, CO 2 remains locked in limiting its escape. This mechanism is facilitated by the flexibility of organic ligands and the pivot motion of cluster units. In situ powder X-ray diffraction revealed that the crystal structure change is negligible before and after CO 2 capture, unlike gate-opening coordination networks. The uncovered CO 2 sorption and retention ability paves the way for the design of sorbents based on isolated voids.