Guest-Selective Recognition in a Flexible Bipyridinium-Based Framework in a Reversible Crystal-to-Crystal Fashion

A flexible bipyridinium-linker-based porous host framework with electron-accepting pore surface, namely, [Zn₂ (L)(pmc)_1.5 ]⋅12 H₂ O (1; L⋅Cl₂ =1,1'-[1,4-phenylene-bis(methylene)]bis(4,4'-bipyridinium) dichloride, H₄ pmc=pyromellitic acid) exhibits recognition of phenol and aromatic amine guests based on adsorbent-adsorbate charge-transfer interactions. Significantly, the resultant guest-encapsulated complexes 1@Guests can all be characterized by single-crystal X-ray diffraction. The host framework undergoes a reversible single crystal-to-single crystal transformation in response to the inclusion of different guests with flexible torsional motions of the hexagonal ring and the trapezoid-shaped bipyridinium groups. Such recognition can be visibly monitored and detected by obvious color changes. The host framework could also be recovered, and this suggested that guest sorption/desorption is reversible and that the host framework could be reused in potential applications. This work may provide an effective way to develop porous materials with special emphasis on applications involving guest recognition.