Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid

Two Ln^III ions are sandwiched by dinuclear Co^II building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H₆L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co₄Ln₂(LH_2.5)₂(H₂O)₄]·(ClO₄)₆·NO₃·nH₂O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO₃^? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency.