Self-assembly of tripyrazolate-linked [M 6 L 2 ] cages for the selective sensing of HSO 3 - and gaseous SO 2 by turn-on fluorescence.

Owing to their structural designability and tuneable properties, supramolecular metal-organic complexes have recently emerged as promising candidates for the sensing and detection of molecules and anions. Herein, we synthesised three tripyrazolate-linked [M 6 L 2 ] metallocages with the formulas [(bpyPd) 6 L 2 ](NO 3 ) 6 (1), [(dmbpyPd) 6 L 2 ](NO 3 ) 6 (2), and [(phenPd) 6 L 2 ](NO 3 ) 6 (3) (H 3 L = tris(4-(5-(trifluoromethyl)-1 H -pyrazol-3-yl)phenyl)amine, bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethylbipyridine, phen = 1,10-phenanthroline). Crystallography revealed that metal-directed coordination and the bidentate chelate behaviour of the ligand induced the self-assembly of supramolecular metal-organic cages. Notably, these cages were employed as turn-on fluorescence sensors for SO 2 and its derivative (HSO 3 - ) through a disassembly mechanism. Cages 1, 2, and 3 showed a highly selective and sensitive detection of HSO 3 - over other common anions in aqueous solutions and of SO 2 gas over other common gasses, with an excellent anti-interference ability. These metallocages were subsequently applied as sensors in environmental and biological samples. This study not only enriches the ongoing research on metal-organic supramolecular materials but also facilitates the future preparation of stimuli-responsive supramolecular coordination complexes.