| Phthalocyanine and its derivatives are typical dyes in the near-infrared region.The strong Q-band absorption caused by theπ-π*transition has become the focus of researchers.And because of its easily modifiedπ-electron system,high thermal stability and chemical stability,it is an ideal sensitizer for dye-sensitized solar cells.However,the spectral response band gap of phthalocyanine is narrow and it is easy to causeπ-πaccumulation and poor solubility,which restrict its further development.Binuclear phthalocyanine formed by anthraquinone oxygen bridge semi-flexible group not only enlarged the macrocyclic conjugate structure to a certain extent,but also greatly improved the solubility of phthalocyanine.In this paper,the anthraquinone oxygen bridge was used as the connecting group to connect two mononucleate phthalocyanine molecules.While enhancing electron flow between the molecules,the two mononucleate phthalocyanine molecules could also induce spectral absorption in the range of 400-600nm,making up for the defect of no absorption in the spectrum of phthalocyanine at 400-600nm.At the same time,a semi-flexible oxygen bridge was used to connect two mononucleic phthalocyanine molecules,so that the two phthalocyanine molecules were connected at different angles and in different planes,which greatly reduced the accumulation phenomenon caused byπ-πconjugate of the phthalocyanine molecules.Based on 1,5-dihydroxyquinone,4-nitrophthalonitrile,3,5-dimethylphenol,β-naphthol,tert-butylphenol,p-methylphenol and p-methylthiophenol,six phthalonitrile derivatives were synthesized by electrophilic substitution reaction:1,5-di[4-（1,2-dinitrile-based）phenoxy]anthraquinone（1）,4-（3）,5-dimethylphenoxy)phthalonitrile（2）,4-（β-naphthaleneoxy）phthal onitrile（3）,4-（4-tert-butylphenoxy）phthalonitrile（4）,4-（p-methylphenoxy）phthalonitrile（5）,4-（p-methylphenylthibenzodiazepines（6）.then,1,5-di[4-（1,2-dionitrile-based）phenoxy]anthraqui nones and five other phthalonitrile derivatives modified by oxygen bridge functional groups are polymerized under DBU catalysis to form five symmetrical binuclear phthalocyan ines:9（10）,16（17）,23（24）-tri[3,5-dimethylphenoxyphenoxy]-2（3）-（1,5-dioxoquinone）binuclear zinc phthalocyanines（7）,9（10）,16（17）-anthranylβ-（23）-naphthalene（8）,9（10）,16（17）,23（24）-tri[4-tert-butylphenoxy]-2（3）-（1,5-dioxythranquinone）binuclear zinc phthalocy anine（9）and 9（10）,16（17）,23（24）-tri[p-methylphenoxy]-2（3）-（1,5-dioxythranthrone）dinucl ear zinc phthalocyanine（10）,9（10）,16（17）,23（24）-tri[p-methylthioxythiohydrin（3）-quinone）-quinone（1）-quinone)The structure characterization,spectroscopic analysis and electrochemical mea surements of these five new phthalocyanines were carried out.Trying to be consistent.Compared with unsubstituted phthalocyanine,the five kinds of binuclear phthalocyanine showed different levels of red shift in the Q band through ultraviolet-visible spectroscopy,in which the oxygen-bridge-connected substituents are red-shifted about 10 nm,the sulfur-bri dge-connected substituents are red-shifted about 20 nm,and absorption is produced at 400-600 nm,which makes up for the blind absorption area of phthalocyanines in this range.DMF was used as solvent to configure 0.1×10-5-1.0×10-55 mol·L-1different concentrations of 5 bin-uclear phthalocyanines.it was found that the novel phthalocyanines existed as monomers in different concentrations of DMF solutions withoutπ-πconjugated stacking.Cyclic voltammetry indicates that 5 the LUMO and HOMO orbital energy levels of the binuclear phthalocyanine match the TiO2 conduction band and the redox potential of the I3-/I-used as potential photosensitizers for dye-sensitized solar cells.by thermogravimetric analysis of the thermal stability of compounds（10）,（11）,the compounds showed excellent stability within400℃. |
