Sensitive and Specific Guest Recognition through Pyridinium‐Modification in Spindle‐Like Coordination Containers

Abstract An elaborately designed pyridinium‐functionalized octanuclear zinc(II) coordination container 1‐Zn was prepared through the self‐assembly of Zn2+, p‐tert‐butylsulfonylcalix[4]arene, and pyridinium‐functionalized angular flexible dicarboxylate linker (H2BrL1). The structure was determined by a single‐crystal X‐ray diffractometer. 1‐Zn displays highly sensitive and specific recognition to 2‐picolylamine as revealed by drastic blueshifts of the absorption and emission spectra, ascribed to the decrease of intramolecular charge transfer (ICT) character of the container and the occurrence of intermolecular charge transfer between the host and guest molecules. The intramolecular charge transfer plays a key role in the modulation of the electronic properties and is tunable through endo‐encapsulation of specific guest molecules.