Post-Synthetic Modification of Nonporous Adaptive Crystals of Pillar[4]arene[1]quinone by Capturing Vaporized Amines

Postsynthetic modification in crystalline solids without disruption of crystallinity is very important for exerting control that is unattainable over chemical transformation in solution. This has been achieved in porous crystalline frameworks via solid-solution reactions to endow them with multiple functions. However, this is rather rare in nonporous molecular crystals, especially via solid–vapor reactions. Herein, we report unique solid–vapor postsynthetic modification of nonporous adaptive crystals (NACs) of a pillar[4]­arene[1]­quinone (EtP4Q1) containing four inert 1,4-diethoxybenzene units and one active benzoquinone unit. Amine vapors that can be physically adsorbed by EtP4Q1 NACs react with the EtP4Q1 backbone via Michael addition with in situ formation of new crystal structures. First, amines are physically adsorbed into cavities of EtP4Q1 molecules and slowly react due to their juxtapsition with the benzoquinone units. Amines that are too bulky to enter EtP4Q1 NACs do not react. Moreover, the process displays both reactant-size and -shape selectivities because of the rigid cavity of EtP4Q1 and the different binding strengths of various amines with EtP4Q1.