周环取代基对酞菁在不同基质中光谱性能的影响

Effect of Pericyclic Substitutes on the Spectral Properties of Phthalocyanine in Different Substrates

将不同周环取代基的金属酞菁均采用溶胶-凝胶(Sol-gel)工艺法掺入二氧化硅(SiO2)凝胶玻璃基质中,制备了金属酞菁掺杂的复合凝胶玻璃。系统研究了酞菁铅系列、酞菁铝系列和酞菁锌系列中不同周环取代基种类和位置对酞菁在N,N-二甲基酰胺(DMF)溶液和二氧化硅凝胶玻璃基质中的紫外-可见吸收光谱的影响,以检测不同周环取代基的种类和位置对酞菁在不同基质中的存在状态及其影响因素。首先研究了周环取代基种类的影响:在DMF溶液中,不同周环取代基-CP、-OAr、 t-Bu的引入,均可使大环π电子形成更大的共轭体系,使最大电子吸收波长产生红移;在复合凝胶玻璃中,掺杂金属酞菁以多聚物的形式存在,使其紫外-可见光谱中的特征吸收峰均变得弥散;研究了周环取代基位置的影响:对酞菁铝系列研究了周环取代基-OAr分别在α和β位时,α-AlTPOPcCl和β-AlTPOPcCl在DMF溶液和二氧化硅复合凝胶玻璃中的紫外-可见吸收光谱,结果表明:在DMF溶液中,由于电子共轭效应,α位的取代基相比β位其特征峰有所红移;在复合凝胶玻璃中,α-AlTPOPcCl的紫外-可见吸收光谱与其在DMF溶液中几乎相同,说明α-AlTPOPcCl在这两种基质中以单体形式存在,而β-AlTPOPcCl在复合凝胶体系中吸收光谱峰型弥散,说明该酞菁在复合体系中多以团聚体形式存在。研究结果为进一步研究酞菁掺杂复合凝胶玻璃的光学性能奠定了基础,为非线性光限幅性能材料及器具的研究奠定了理论基础。

Metal phthalocyanines with different peripheral substituents were doped into silica(SiO2)gel glass matrix by the Sol-gel process to prepare metal phthalocyanine doped composite gel glass.The effects of the types and positions of different cyclic substituents in lead phthalocyanine series,aluminum phthalocyanine series,and zinc phthalocyanine series on the UV visible absorption spectra of phthalocyanine in DMF solution and silica gel glass matrix were systematically studied to detect the existence status of phthalocyanine in different matrices and the influencing factors of the types and positions of different cyclic substituents.Firstly,the influence of the types of pericyclic substituents was studied:in DMF solution,the introduction of different pericyclic substituents-CP,-OAr,t-Bu can lead to the formation of a larger conjugated system of largeπelectrons,resulting in a red shift in the maximum electron absorption wavelength;In the composite gel glass,the doped metal phthalocyanine exists in the form of polymer,which makes the characteristic absorption peaks in the ultraviolet-visible spectrum become dispersed.Secondly,the influence of the position of cyclic substituents was studied:for the aluminum phthalocyanine series,the cyclic substituents OAr were studied,respectivelyαandβBit time,α-AlTPOPcCl and Ultraviolet-visible absorption spectrum ofβ-AlTPOPcCl in DMF solution and silica composite gel glass.The results indicate that in DMF solution,due to the electron conjugation effect,αCompared to the substituent of positionβ,The characteristic peak has a redshift.In composite gel glass,The UV visible absorption spectra ofα-AlTPOPcCl are almost identical to those in DMF solution,indicating thatα-AlTPOPcCl exists as a monomer in these two matrices.The absorption spectra ofβ-AlTPOPcCl dispersed in the composite gel system,indicating that the phthalocyanine mainly existed in aggregate in the composite system.The above research results lay the experimental foundation for further research on the optical properties of phthalocyanine-doped composite gel glass and also laid the theoretical foundation for the research on nonlinear optical limiting materials and devices.