Chromic and Fluorescence-Responsive Metal–Organic Frameworks Afforded by N-Amination Modification

Sensory materials that show color and/or fluorescence changes in response to specific gases or vapors have important applications in many fields. Here, we report the postsynthetic preparation of novel sensory metal–organic frameworks (MOFs) and their multiple responsive properties. Through postsynthetic N-amination, the 2,2′-bipyridyl spacers in a Zr(IV) MOF are partially transformed into N-aminobipyridinium. The new MOF (Zr-bpy-A) shows chromic behavior toward ammonia and amines because the electron-deficient pyridinium groups form charge-transfer complexes with amino moieties. It also shows a unique chromic response to formaldehyde owing to the Schiff-base condensation with the N-amino groups. Furthermore, the N-amino group can be used to graft different polycyclic aromatic hydrocarbons, which endow the MOF with strong fluorescence of variable colors and afford a high-contrast fluorescence response to ammonia/amines and formaldehyde associated with the chromic response. The presence of the unquaternized bipyridyl group also leads to a fluorescence response to HCl. The multiple responsive behaviors hold appeal for applications in sensing, switching, and antifake marking, which are illustrated with a test paper and writing ink.