Less is More: A Shortcut for Anionocages Design Based on (RPO₃²⁻)‐Monourea Coordination

Abstract Anionocages have been developed as a unique family of hydrogen bonded cages. However, strategies for constructing anionocages are mainly limited to that based on (PO 4 3− )‐bisurea coordination, neither the ligands nor the anions lack the simplicity and diversity of the maturely developed analogues based on metal coordination (i.e. metallocage). We report herein a more simple strategy for anionocages design based on (RPO 3 2− )‐monourea coordination, utilizing monourea rather than bisurea as the hydrogen binding donor, and RPO 3 2− rather than PO 4 3− as the acceptor. Two fluorescent, quadruple helicate anionocages were constructed by a bis‐monourea ligand, and dianions PhOPO 3 2− ( H 1 ) or HOPO 3 2− ( H 1A ), respectively, which were capable of encapsulating a series of cation guests. As revealed by molecular modeling, H 1 features remarkable guest‐adaptive cavity breathing without change of the quadruple helicate topology, which allowed the encapsulation of different sized guests in an “induced fit” manner.