Kinetic Assembly of Porous Coordination Networks Leads to Trapping Unstable Elemental Allotropes

Kinetic assembly is an important method for obtaining desired materials in chemical synthesis and material sciences. However, the application of this strategy to porous coordination networks has been limited. We highlight the kinetic assembly of porous coordination networks, which promote the production of interactive pore sites. These sites can activate or stabilize different guest molecules. The properties of interactive pores are exemplified by iodine chemisorption and small sulfur encapsulation. Using the interactive feature of these pores, we were able to trap small sulfur allotropes, such as S2, cyclo-S3, bent-S3, and S6, demonstrating their importance for the stabilization of unusual elemental species. Furthermore, several reactive elemental allotropes could also be incorporated into the interactive pores. Herein, we address the important aspects of creating interactive pore sites by kinetic assembly of porous coordination networks and present detailed case-by-case studies of small allotrope encapsulation.