Syntheses And Chemical Sensing Of Luminescent Metal Organic Frameworks Based On Triphenylamine

As a new type of porous material,metal organic frameworks?MOFs?have broad application prospects in chemical sensing.In this thesis,an organic ligand?tris?4-?1H-imidazol-1-yl?phenyl?amine?TIPA and seven kinds of MOFs with three different topologies were synthesized.MOFs crystals were characterized by single crystal,Nuclear Magnetic Resonance,Powder X-ray diffraction,etc.;fluorescence performance and selective detection performance for organic molecules and ions in water were performed.1.[Mn?TIPA??ndc??H2O?]n?MOF-1?,[Mn2Cl2?TIPA?2?oba?]n?MOF-2?and[Mn3O?TIPA??oba?3]n?MOF-3?were synthesized by the self-assembly of TIPA,1,4-ndc?1,4-naphthalenedicarboxylic acid?or 4,4'-H2oba?4,4'-oxybisbenzoic acid?and Mn Cl2?4H2O.Single crystal diffraction shows that MOF-1?MOF-2?MOF-3 are all two-node network structures and MOF-3 is double penetration.Among them,MOF-1 and MOF-2 are six-coordinate octahedral structures with a single Mn atom as the core,while MOF-3 is a pentahedron with SBU with Mn3O?CO2?6 unit as the core.It is calculated that the porosity of MOF-1?MOF-2?MOF-3 is 5.8%,25.6%,and 28.5%respectively;fluorescence tests show that all three compounds emit blue light,and MOF-1 was subjected to selective detection of metal anions and antibiotics in water,and the results showed that MOF-1 can be used as a probe with good selectivity and high sensitivity.2.[Cd2?TIPA?2?bpodc?2]n?MOF-4?,[Cd2?TIPA?2?oba?2]n?MOF-5?,[Cd2?TIPA?2?oba??NO3?2]n?MOF-6?were synthesized by the self-assembly of TIPA,bpodc?4,4'-benzophenonedicarboxylic acid?or 4,4'-H2oba?4,4'-oxybisbenzoic acid?and Cd?NO3?2·4H2O or Cd?Cl O4?2·6H2O.Single crystal diffraction shows that MOF-4?MOF-5?MOF-6 are both two-node network structures and MOF-4 and 5 are double penetration.Among them,MOF-4 and 5 have the same topology?two six-coordinate octahedrons with two different cadmium atoms as the core?,while MOF-6 is a seven-coordinate octahedron with a single cadmium atom as the core.It is calculated that the porosity of MOF-4?MOF-5?MOF-6 is 18.6%,19.5%,and 24.2%,respectively;fluorescence tests show that MOF-4 emits yellow-green light,while MOF-5 and MOF-6 emit blue light.Selective detection of water and organic solvents for MOF-4 and 5,In addition,MOF-5 was tested for metal anions and cations.The results show that MOF-5 can be used as a probe for detecting Fe³⁺,Cr O₄^2-and Cr₂O₇^2-.3.[Zn4O?TIPA??oba?3]?MOF-7?was synthesized by connecting TIPA,Zn?NO3?2·6H2O and 4,4'-H2oba.Single crystal diffraction shows that MOF-7 is a two-node network structure with double penetration.It is based on the metal cluster SBU of Zn4O?CO2?6.After calculation,the porosity of MOF-7 is 13.5%;the fluorescence test shows that it emits blue light,and the MOF-7 is subjected to selective detection of metal anions and cations in water.The results show that MOF-7 can be used as a probe for detecting Fe³⁺,Cr O₄^2-and Cr₂O₇^2-.