Selective Supramolecular Recognition of Nitroaromatics by a Fluorescent Metal-Organic Cage Based on a Pyridine-Decorated Dibenzodiaza-Crown Macrocyclic Co(II) Complex

Two isomorphous fluorescent (FL) lantern-shaped metal-organic cages 1 and 2 were prepared by coordination directed self-assembly of Co(II) centers with a new aza-crown macrocyclic ligand bearing pyridine pendant arms (Lpy). The cage structures were determined using single-crystal X-ray diffraction analysis, thermogravimetric, elemental microanalysis, FT-IR spectroscopy, and powder X-ray diffraction. The crystal structures of 1 and 2 show that anions (Cl- in 1 and Br- in 2) are encapsulated within the cage cavity. 1 and 2 bear two coordinated water molecules that are directed inside the cages, surrounded by the eight pyridine rings at the bottom and the roof of the cage. These hydrogen bond donors, pi systems, and the cationic nature of the cages enable 1 and 2 to encapsulate the anions. FL experiments revealed that 1 could detect nitroaromatic compounds by exhibiting selective and sensitive fluorescence quenching toward p-nitroaniline (PNA), recommending a limit of detection of 4.24 ppm. Moreover, the addition of 50 mu L of PNA and o-nitrophenol to the ethanolic suspension of 1 led to a significant large FL red shift, namely, 87 and 24 nm, respectively, which were significantly higher than the corresponding values observed in the presence of other nitroaromatic compounds. The titration of the ethanolic suspension of 1, with various concentrations of PNA (>12 mu M) demonstrated a concentration-dependent emission red shift. Hence, the efficient FL quenching of 1 was capable of distinguishing the dinitrobenzene isomers. Meanwhile, the observed red shift (10 nm) and quenching of this emission band under the influence of a trace amount of o-and p-nitrophenol isomers also showed that 1 could discriminate between o-and p-nitrophenol. Replacement of the chlorido with a bromido ligand in 1 generated cage 2 which was a more electron-donating cage than 1. The FL experiments showed that 2 was partially more sensitive and less selective toward NACs than 1.

Automated summary

Two fluorescent metal-organic cages, 1 and 2, were synthesized by self-assembly of Co(II) centers with a new macrocyclic ligand. The structures of the cages were determined using various analytical techniques. Cage 1 exhibited selective and sensitive fluorescence quenching towards p-nitroaniline, detecting it at a concentration as low as 4.24 ppm. Cage 2, with a bromido ligand instead of chlorido, showed higher sensitivity but lower selectivity towards NACs than cage 1.