Synthesis And Properties Of Benzophenone Oxygen Bridged Binuclear Phthalocyanine

Phthalocyanine and its derivatives are typical near-infrared dyes,with strong Q-band absorption,easy-to-modify structural features,high thermal stability and chemical stability,and are ideal dye sensitizers.Sensitizing dyes for solar cells.However,the spectral response band gap of phthalocyanine is relatively narrow and the solubility is poor.These factors restrict its further development.The dinuclear phthalocyanine formed by connecting semi-flexible groups with benzophenone oxygen bridge is expected to expand its conjugated structure system and improve the solubility of phthalocyanine.4-nitrophthalonitrile and 4,4’-dihydroxybenzophenone,β-naphthol,α-naphthol,p-tert-butylphenol,p-methoxyphenol,p-methylthiophenol and The reaction of p-hydroxybenzoic acid produces seven phthalonitrile derivatives:1,5-bis[4-（1,2-dicyano）phenoxy]benzophenone,4-（β-naphthyloxy）)Phthalonitrile,4-（α-naphthyloxy）phthalonitrile,4-（4-tert-butylphenoxy）phthalonitrile,4-（p-methoxyphenoxy）)Phthalonitrile,4-（p-methylphenylthio）phthalonitrile,4-（p-carboxyphenoxy）phthalonitrile.Then 1,5-bis[4-（1,2-dicyano）phenoxy]benzophenone and six other precursors and zinc acetate were added to DBU（1.8-diaza heterocycle[5,4,0]Undecene）catalyzed synthesis of six benzophenone oxygen bridged binuclear phthalocyan-ines:9（10）,16（17）,23（24）-tris（β-naphthyloxy）-2（3）-（4,4’-Dioxybenzophenone）binuclear zinc phthalocyanine（bi-βPC）,9（10）,16（17）,23（24）-tris（α-naphthyloxy）-2（3）-（4,4’-Dioxybenz-ophenone）binuclear zinc phthalocyanine（bi-αPC）,9（10）,16（17）,23（24）-tris（4-tert-butylben-zene）Oxy)-2（3）-（4,4’-dioxybenzophenone）binuclear zinc phthalocyanine（bi-TPC）,9（10）,16（17）,23（24）-three（pair Methoxyphenoxy）-2（3）-（4,4’-dioxybenzophenone）binuclear zinc phthalocyanine（bi-MOPC）,9（10）,16（17）,23（24）-Tris（p-methylphenylthio）-2（3）-（4,4’-dioxy-benzophenone）binuclear zinc phthalocyanine（bi-MTPC）,9（10）,16（17）,23（24）-Tris（p-carb-oxyphenoxy）-2（3）-（4,4’-dioxybenzophenone）binuclear zinc phthalocyanine（bi-CPC）.Six kinds of benzophenone oxygen bridged binuclear phthalocyanine compounds were characterized by FT-IR,¹HNMR,elemental analysis,UV-Vis,and cyclic voltammetry.Through ultraviolet-visible spectroscopy test,bi-βPC,bi-αPC,bi-TPC,bi-MOPC,bi-MTPC and bi-CPC six kinds of benzophenone oxygen bridged binuclear phthalocyanine Q bands have different degrees of red shift,Respectively,redshift 8,16,9,13,12,32nm.Using DMF as the solvent to configure the six kinds of benzophenone oxygen bridged dinuclear phthalocyanine solutions with different concentrations of 0.1×10-5-1.0×10-5mol·L-1,the experiment shows that six kinds of benzophenone oxygen bridged dinuclear phthalocyanines were synthesized The cyanine exists as a monomer in the DMF solution in this range and does not aggregate.Cyclic voltammetry shows that the LUMO and HOMO orbital energy levels of six benzophenone oxygen bridged binuclear phthalocyanines match the conduction band of TiO₂and the redox potential of I₃^-/I^-,which can be used as potential photosensitizers of dye-sensitized solar cells Agent.The benzophenone oxygen bridge connects two mononuclear phthalocyanine molecules.On the one hand,it enhances the electron flow between the phthalocyanine molecules,and on the other hand,it absorbs at 200～400nm and enhances the weak B-band absorption.The dinuclear phthalocyanine formed by connecting the semi-flexible group of benzophenone oxygen bridge makes two mononuclear phthalocyanine molecules exist in different planes,which greatly weakens the aggregation of phthalocyanine.The phthalocyanine molecules can be monomers The form is effectively loaded on the surface of titanium dioxide with various morphologies.