Synthesis And Properties Of The Binuclear Zinc Phthalocyanine Formed By Droxynaphthyl Bridge

Phthalocyanines（Pcs） are a kind of function material with macrocyclic conjugated structure, which have excellent thermal and chemical stability.Phthalocyanines are typical near-infrared dye, possessing remarkable photoelectric properties and exhibiting strong absorptions in ultra violet（UV） and near-infraredregion. Binuclear phthalocyanineconnected together by two phthalocyanine molecules through a bridging group whichexcellent performance with a single-core phthalocyanine.Introduction of a metal ion and different organic groups to widen the range of light-absorbing dye to improve light absorption intensity can also be improved solubility, aggregation, improve phthalocyanine photoelectric conversion efficiency.Select droxynaphthyl as the bridging groups, can improve the stability of phthalocyanine and expand conjugated structure.In this artical wedesigned and synthesized a series of binuclear phthalocyanines, using naphthalene to connect two phthalocyanines, which the substituents were introduced to the phthalocyanine core through oxygen bridge, in one structure. And the UV–Vis spectroscopy, solubility, aggregation behavior, thermal stability,andthe reduction and oxidation behavior were investigated.Liquid phase method,Phthalonitrile derivatives 1,5-bis(4-（1,2-dimethylphenoxy） naphthyl, 4-（4-methyl-coumarin-7-oxy）phthalonitrile, 4-（8-quinoline-oxy）phthalonitrile, 4-carboxy-phenoxy-phthalonitrile, 4-（α-naphthyloxy）phthalonitrile were synthesized by 4-nitrophthalonitrile and 1,5-dihydroxynaphthalene naphthol, 7-hydroxy-4-methylcoumarin, 8-quinolinol, p-hydroxybenzoic acid, α-naphthol respectively.Five kinds of phthalonitrile derivatives 9（10）,16（17）,23（24）–tris（4-methyl-coumarin-7yloxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine, 9（10）,16（17）,23（24）–tris（8-quinolinyloxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine, 9（10）,16（17）,23（24）-tris（p-carboxyphenoxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine, 9（10）,16（17）,23（24）-tris（α-naphthoxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine synthesis of the corresponding binuclear phthalocyanine compound under 1,8-diazabicyclo [5.4.0] undec-7-ene（DBU） catalysis.The five phthalocyanineprecursors and four binuclear phthalocyanines were fullycharacterized by Fourier transform infrared spectroscopy, elemental analyses and 1Hnuclear magnetic resonance, The characterization data of the new compounds was consistent with the assigned formula.The UV–Vis spectroscopy of the four binuclear phthalocyaninesshowed strongabsorption at 677-690 nm redshifted 10-20 nm compared with the unsubstituted zinc phthalocyanine, the target phthalocyanines had no aggregation in DMF solution, 9（10）,16（17）,23（24）-tris（4-methyl-coumarin-7yloxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine and 9（10）,16（17）,23（24）-tris（α-naphthoxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine exhibited the broadest absorption regions among the four binuclearphthalocyanines. As 9（10）,16（17）,23（24）-tris（4-methyl-coumarin-7 yloxy）-2（3）-（1,5-naphthalene） binuclear zinc phthalocyanine case Thermogravimetric Analysis was carried out to study the thermal stability of the target compounds, the result of the measurements indicated that all the binuclear phthalocyanines exhibited good thermal stability in temperature over 200 ℃.And the cyclic voltammetry experiments were carried out to study the reduction and oxidation behavior, proved that the binuclear phthalocyanineshave higher LUMO levels and lower HOMO levels, which matched with the conduction-band-edge energy level of the TiO₂, illuminated the binuclear phthalocyanines have the photoelectric properties and it is expected as a dye sensitizer use in solar cells.