An Imine-Linked Metal-Organic Framework as a Reactive Oxygen Species Generator.

ABSTRACT

A new metal-organic framework (MOF) with both coordination linkages and covalent linkages is prepared by coordinating CuI with pyrazolate for an aldehyde-functionalized trinuclear complex, and subsequent imine condensation with p-phenylenediamine, a reaction typical for covalent organic framework (COF) synthesis. This MOF×COF collaboration yields FDM-71 with honeycomb layers stacked in eclipsed fashion. After dissociating the CuI -pyrazolate coordination in FDM-71, the obtained organic components carry the information of structural defects, and thus vacancy identity (aldehyde-based unit vacancy and amine-based unit vacancy) and concentration are definitely resolved. Further to the redox catalytic activity inherited from the complex, FDM-71 features effective photosensitizing activity. The two functions integrated in one well-defined structure is demonstrated by its high efficiency in decomposing H2 O2 and consequent excitation of O2 to reactive oxygen species.