Zinc(II)-MOF: A Versatile Luminescent Sensor for Selective Molecular Recognition of Flame Retardants and Antibiotics.

Abstract

An exceptional Zinc(II)-organic framework with the formula [{Zn(L4-py)(bdc)}·DMF]n (Zn-MOF) has been constructed solvothermally using a novel linker L4-py {2,7-bis(3-(pyridin-4-ylethynyl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone}, coligand H2bdc (1,4-benzenedicarboxylic acid), and ZnBF4·xH2O. The ligand L4-py has been fabricated after functionalization of NDA (1,4,5,8-naphthalenetetracarboxylic dianhydride) core with 3-(pyridin-4-ylethynyl)phenyl group. The single-crystal X-ray analysis reveals that Zn-MOF exhibits a comprehensive three-dimensional (3D) framework architecture and features (4)-connected uninodal dia; 4/6/c1; sqc6 topology with point symbol {66} and two-dimensional (2D) + 2D, parallel polycatenation. Notably, Zn-MOF displayed excellent fluorescence phenomenon and stability in water as well as in methanol solvents and was harnessed as a versatile sensor, demonstrating selective and sensitive molecular recognition of flame retardants and antibiotics. Notably, Zn-MOF displayed 57 and 49.5% quenching efficiency for the flame-retardant pentabromophenol (PBP) and 3,3',5,5'-tetrabromobisphenol A (TBPA), respectively. Whereas an outstanding 90% quenching efficiency was observed for antibiotics, tetracycline (TC) and secnidazole (SD). The mechanistic investigations of this luminescence quenching suggest that this might be primarily occurring via the Fourier resonance energy transfer (FRET) and photoinduced electron transfer (PET) mechanisms, which might be assisted by the competitive absorption and host-guest interactions. The π-electron-rich framework structure of sensor Zn-MOF activates this mechanism.