Unusual NH Activation of 2‐Aminopyrimidine: Supramolecular Assembly into an Ag I Metal–Organic Framework

A rare example of coordination at the amino group of NH 2 pym (2‐aminopyrimidine) relevant to NH activation is described that leads to a novel Ag I –imide 3D metal–organic framework (MOF). The coordination of Ag I to NH 2 pym produced an electron‐withdrawing effect and thus increased its acidity, which facilitated the NH activation and the subsequent formation of the Ag–imide bond. A cooperative metalation/deprotonation process for the NH activation of NH 2 pym is suggested. Interestingly, photoluminescence of 1 is switched on at the low temperature of 77 K.