Single-crystalline molecular flasks: chemical transformation with bulky reagents in the pores of porous coordination networks

1The pore channels facilitate increased mobility and rapid diffusion of included guest molecules. Large organic molecules can readily enter into the pores via guest exchange. In this sense, the pore interior is a pseudo-solution state where chemical reactions may proceed as in a solution, yet can be directly analyzed by crystallography. Here, we show that single-crystal-tosingle-crystal chemical reactions with large, common reagents proceed quite smoothly inside the pores of the network. Taking advantage of the network’s robust crystallinity, we succeeded in the acylation and ureidation of aromatic amines and imine formation from aromatic aldehydes within a single crystal. The pores of the network complexes thus serve as “single crystalline molecular flasks”. 2 In related studies, we have reported the preliminary results of the diffusion of aldehydes into the pores of porous networks to form imine. 3