Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metal-organic framework

Reported herein is a thermally-promoted, post-synthetic modification of a zinc metal-organic frameworks pore surface. Sulfoxide tag groups are modified by conventional heating via Pummerer-type chemistry and elimination to aldehyde groups. Simultaneously, a minor competing disproportionation reaction occurs, creating sulfide and sulfone tag groups enhancing the complexity of the pores. The thermal process is gentle, with crystallinity fully maintained, and results in a higher surface area and pore volume for the modified framework.