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Inspired by the signal transduction function of organophosphates in biological systems, bioactive organophosphates were utilized for the first time as chiral nodes to dictate the stereoselective assembly of hydrogen‐bonded anionic cages. Phosphonomycin (antibiotics), tenofovir (antivirals), adenosine monophosphate (natural product, AMP) and clindamycin phosphate (antibiotics) were assembled with an achiral bis‐monourea ligand, thereby leading to the stereoselective formation of quadruple or triple helicates. The extent of the stereoselectivity could be enhanced by either lowering the temperature or adding stronger‐binding cations as templates. With the chiral anionic cages as the host, some enantioselectivity was achieved when binding chiral quaternary ammonium cations. [ABSTRACT FROM AUTHOR]

Anionocages have been developed as a unique family of hydrogen bonded cages. However, strategies for constructing anionocages are mainly limited to that based on (PO43−)‐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 (RPO32−)‐monourea coordination, utilizing monourea rather than bisurea as the hydrogen binding donor, and RPO32− rather than PO43− as the acceptor. Two fluorescent, quadruple helicate anionocages were constructed by a bis‐monourea ligand, and dianions PhOPO32− (H1) or HOPO32− (H1A), respectively, which were capable of encapsulating a series of cation guests. As revealed by molecular modeling, H1 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. [ABSTRACT FROM AUTHOR]