The construction of pore-functionalized,charged metal-organic frameworks(MOFs)promises criticalfluorosensing of harmful organo-aromatics,toxic pollutant adsorption,and luminescent-ink based antic ounterfeiting applica...The construction of pore-functionalized,charged metal-organic frameworks(MOFs)promises criticalfluorosensing of harmful organo-aromatics,toxic pollutant adsorption,and luminescent-ink based antic ounterfeiting applications.We report the strategic construction of a non-penetrated framework,CSMCRI-4(CSMCRI=Central Salt&Marine Chemicals Research Institute),from an electron-rich tricar boxylate ligand and the lightest metal-ion,which possesses anionic[Li_(2)(COO)_(4)]secondary building units(SBUs)and unbound oxygen atom decorated porous channels.The activated MOF(4a)displays extremely selective and ultrafast luminescent sensing of the lethal 2,6-dichloro-4-nitroaniline(DCNA)pesticide and the nitrofurazone(NZF)antibiotic with notable quenching and low limits of detection.It is imperative to stress the outstanding reusability of the MOF toward multicyclic sensing of both the organo-toxins.The reversibility of the host-vip interplay between the framework and individual analytes instigatesfluor escence“off-on-off”switching,which is demonstrated by handy paper-strip monitoring.Density func tional theory(DFT)calculation portrays unprecedented reshuffing of the molecular orbital energy levels in the electron-rich MOF by each nitro-organic,and verifies the framework-analyte supramolecular inter actions.The extra-framework cations and free oxygen-atom affxed pore surface benefits selective encapsulation and sensitization of Tb^(3+)ions,which sharply change the emission color to green.The blue emission of the pristine MOF and modulated light emission in the Tb^(3+)-doped material are utilized as highly regenerable luminescent-inks for vivid acronym encryption.The framework further illustrates charge-exclusive reversible adsorption of the toxic,cationic methylene blue(MB^(+))dye through bi-phasic colorimetric variation.DFT calculation precisely delineates the replacement of the pore-occluded vip by MB+,and explicitly validates its pore-fitting induced size selectivity over other dyes.展开更多
基金the DST-SERB(grant no.ECR/2016/000156)the CSIR(grant no.MLP-0028)+3 种基金N.S.thanks the CSIR,New Delhi,India,for a research fellowship(CSIR grant no:31/028(0252)/2019-EMR-I)M.S.thanks UGC,Delhi,for providing a senior research fellowship.The analytical support from AESD&CIF(CSMCRI)and crystallographic help from Dr.E.Suresh are gratefully acknowledged.CSMCRI com munication no.32/2020R.S.P.gratefully acknowledges the DST-SERB(grant no.SRG/2019/000912)for the financial support,and the High Performance Computing Centre,SRM Institute of Science and Technology for providing the compu tational facilities.
文摘The construction of pore-functionalized,charged metal-organic frameworks(MOFs)promises criticalfluorosensing of harmful organo-aromatics,toxic pollutant adsorption,and luminescent-ink based antic ounterfeiting applications.We report the strategic construction of a non-penetrated framework,CSMCRI-4(CSMCRI=Central Salt&Marine Chemicals Research Institute),from an electron-rich tricar boxylate ligand and the lightest metal-ion,which possesses anionic[Li_(2)(COO)_(4)]secondary building units(SBUs)and unbound oxygen atom decorated porous channels.The activated MOF(4a)displays extremely selective and ultrafast luminescent sensing of the lethal 2,6-dichloro-4-nitroaniline(DCNA)pesticide and the nitrofurazone(NZF)antibiotic with notable quenching and low limits of detection.It is imperative to stress the outstanding reusability of the MOF toward multicyclic sensing of both the organo-toxins.The reversibility of the host-vip interplay between the framework and individual analytes instigatesfluor escence“off-on-off”switching,which is demonstrated by handy paper-strip monitoring.Density func tional theory(DFT)calculation portrays unprecedented reshuffing of the molecular orbital energy levels in the electron-rich MOF by each nitro-organic,and verifies the framework-analyte supramolecular inter actions.The extra-framework cations and free oxygen-atom affxed pore surface benefits selective encapsulation and sensitization of Tb^(3+)ions,which sharply change the emission color to green.The blue emission of the pristine MOF and modulated light emission in the Tb^(3+)-doped material are utilized as highly regenerable luminescent-inks for vivid acronym encryption.The framework further illustrates charge-exclusive reversible adsorption of the toxic,cationic methylene blue(MB^(+))dye through bi-phasic colorimetric variation.DFT calculation precisely delineates the replacement of the pore-occluded vip by MB+,and explicitly validates its pore-fitting induced size selectivity over other dyes.
