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-.