Synthesis,Structure And Properties Of Metal-Thiacalix[4]arene Complexes

p-tert-butylthiacalix[4]arene（H₄TC4A）and its oxidation derivative p-tert-butyl-sulfonylcalix[4]arene（H₄TC4A-SO₂）are cyclic compounds connected by four p-tert-butylphenol units and four sulfur atoms or four sulfonyl groups,respectively.It is easy to form M₄-TC4A or M₄-（TC4A-SO₂）secondary building units（SBU）with transition metal ions under solvothermal conditions because of the abundant coordination sites of H₄TC4A or H₄TC4A-SO₂.M₄-TC4A or M₄-（TC4A-SO₂）SBUs can be further coordinated with nitrogen or carboxyl groups containing auxiliary ligands to obtain diversified and novel complexes.Three metal-calixarene complexes with novel structures were prepared by using H₄TC4A and H₄TC4A-SO₂ and cobalt ions,magnesium ions and manganese ions under solvothermal conditions and assisted ligands.All of the complexes were characterized by PXRD,FT-IR,thermogravimetric（TGA）and so on.The structure of three complexes was determined by X-ray single crystal diffraction.The structural characteristics of the three complexes were analyzed and their fluorescence detection and electroluminescence properties were systematically studied.The main work is as follows:（1）Synthesis and luminescence properties of thiacalix[4]arene-based{Mg₂₄}coordination cageCompound 1 is an octahedral{Mg₂₄}coordination cage{Mg₂₄（TC4A）₆（BTC）₈（H₂O）₆}by utilizing MgCl₂·6H₂O,H₃BTC and H₄TC4A.1 shows excellent luminescence characteristics in both aqueous solution and solid state.At the same time,the cations,anions and small organic molecules in aqueous solution were detected.The luminescence sensing experiment of the system shows that 1 has obvious fluorescence quenching for Fe³⁺,MnO₄^-,nitrobenzene（NB）and 2,4-dinitrophenol（2,4-DNP）in water,and 1 has high sensitivity and selectivity for Fe³⁺,MnO₄^-,NB and 2,4-DNP.Detection limit and quenching constant(K_sv)are 2.65μmol/L,1.73μmol/L 1.10μmol/L,2.06μmol/L,3.08×10⁴ M^-1,4.72×10⁴ M^-1,7.45×10⁴ M^-1,3.98×10⁴ M^-1,respectively.1 shows excellent fluorescence detection performance,and can be used as a high sensitivity fluorescence sensor for detecting Fe³⁺,MnO₄^-,NB and 2,4-DNP.（2）Aggregation-induced electroluminescence of calixarene-based two-dimensional compound limited domain Ir（ppy）₃ for the detection of AβO.Porous two-dimensional compound 2 with ordered structure was prepared by using H₄TC4A-SO₂,isonicotinic acid（INA）and CoCl₂·6H₂O under solvothermal conditions.Two Co₄-（TC4A-SO₂）SBUs,eight INA molecules and four{CoCl₂}units formed a spindle-shaped cage structure,in which four{CoCl₂}units were connected with adjacent spindle-shaped cages,and assembled into porous ordered nanocages and interconnected two-dimensional compounds.Using its spindle-shaped cavity environment and pore environment as a microreactor,the luminescent Tris（2-phenylpyridine）iridium（Ⅲ）（Ir（ppy）₃）was highly-efficiency loaded on the surface of 2,and then achieved the accumulation of Ir（ppy）₃ induced ECL（AIECL）,and in its hydrophobic cavity enrichment of coreactant tripropylamine（TPrA）.The results showed that Ir@2 NRs showed significantly improved ECL efficiency and water dispersion compared with Ir（ppy）₃ monomer.The ECL efficiency and dispersity of Ir（ppy）₃ in aqueous medium were significantly improved.The electrode was modified with the complex of Ir@2 NRs and polyethylenimide（PEI）to assemble platinum nanoparticles and further capture the hair clip H2.The ECL emission of Ir@2NRs/TPrA system was quenched by introducing H₂O₂ into the test solution so that the signal was extinguished.When the target amyloid-beta oligomer（AβO）is present,a large amount of single-stranded S1 is released from the target cycle,triggering chain shift amplification（SDA）on the magnetic bead.The single strand ST output from the SDA reaction will open the hairpin H2 on the electrode surface,triggering a rolling ring amplification（RCA）reaction,generating a large number of long chains rich in G bases,further trapping hemin and forming a hemin/G-tetrad.After the hemin/G-tetrad consumes H₂O₂,the ECL signal is restored,which realizes the sensitive detection of AβO.A novel ECL microreactor loaded with Ir（ppy）₃ and enriched with coreactant TPrA was developed.The high ECL efficiency and excellent dispersibility of Ir@2 NRs provide an excellent ECL sensing platform for bioanalysis,expanding the application of iridium（Ⅲ）complexes in the ECL field.（3）Synthesis and luminescence properties of thiacalix[4]arene-based{Mn₄}cluster compoundsA four-core dumbbell cluster 3 was obtained with manganese ion and H₄TC4A-SO₂.two TC4A-SO₂ molecules were covered on the top and bottom of the four-core manganese cluster at room temperature,3 shows excellent chemical stability and fluorescence characteristics.Therefore,anion and organic small molecule identification experiments for 3 in aqueous solution was conducted.The results of luminescence sensing experiments showed that 3 responded to CrO₄^2-,Cr₂O₇^2-and 2,4-DNP with significant fluorescence quenching.Moreover,3 can recognize CrO₄^2-,Cr₂O₇^2-and 2,4-DNP with excellent anti-interference ability.The detection limits of CrO₄^2-,Cr₂O₇^2-and 2,4-DNP were 1.14μmol/L,0.83μmol/L and 1.34μmol/L,respectively.These results indicate that 3 can be used as a potential fluorescence sensor for the detection of CrO₄^2-,Cr₂O₇^2-and 2,4-DNP.