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Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid
Author(s) -
Tang Qi,
Sun Yao,
Li HongYan,
Wu JiQing,
Liang YuNing,
Zhang Zhong
Publication year - 2019
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4814
Subject(s) - picric acid , chemistry , fluorescence , ligand (biochemistry) , metal ions in aqueous solution , carboxylic acid , tris , förster resonance energy transfer , metal , photochemistry , polymer chemistry , organic chemistry , biochemistry , physics , receptor , quantum mechanics
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 (H 6 L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co 4 Ln 2 (LH 2.5 ) 2 (H 2 O) 4 ]·(ClO 4 ) 6 ·NO 3 ·nH 2 O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO 3 − 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.