Design,Synthesis And Photovoltaic Properties Of Sandwich-Type Phthalocyanine Electron Acceptors

In recent decades,organic solar cell materials have attracted more and more attention of researchers.Except for the first generation of organic solar cell acceptor material copper phthalocyanine,axially substituted phthalocyanine and naphthalocyanine derivatives have been reported as acceptor materials for organic solar cells.Phthalocyanine and naphthalene phthalocyanine molecules have easy coordination holes and multiple active sites.In this work,we have taken three-dimensional phthalocyanines with steric structure as the object of study,and sandwich type double-decker phthalocyanines with peripheral tetraimides substituents rare earth metal complexes were synthesized.The strong electron-withdrawing property of the substituent changes the molecular spectral properties and energy levels greatly.Our research work mainly focuses on the following aspects:(1)Synthesis of sandwich type double-decker rare earth metal phthalocyanine tetraimides and their applications in organic solar cells as acceptors.Using o-xylene as raw material,through six steps of bromination,catalytic oxidation,dehydration,imide alkylation,cyanidation,catalytic cyclization,and coordination,four sandwich type double-decker phthalocyanine rare earth metal complexes 7a-7d with different substituted alkyl groups and central metal atoms were synthesized with total yields of1.3%,1.2%,1.3%and 1.2%,respectively.The four target compounds have good solubility(higher than 20 mg/m L in chloroform),good thermal stability(T_d>325℃),wide film absorption range(600～1000 nm),and low LUMO energy level(-3.91～-3.98 e V),they can be used as acceptor materials for organic solar cells.(2)Synthesis of sandwich type double-decker rare earth metal naphthalocyanine tetraimides and their applications in organic solar cells as acceptors.Using o-xylene as raw material,through nine steps of aromatic cyclobromination,photocatalytic bromination,cyclization,hydrolysis,dehydration,imide alkylation,cyanidation,catalytic cyclization and coordination,four sandwich type double-decker naphthalocyanine rare earth metal complexes 14a-14d with different substituted alkyl groups and central metal atoms were synthesized with total yields of 0.9%,0.8%,0.9%and 0.8%,respectively.The four target compounds have good solubility(higher than20 mg/m L in chloroform),good thermal stability(T_d>290℃),wide film absorption range(600～1200 nm),and low LUMO energy level(-4.02～-4.12 e V),they can be used as acceptor materials for organic solar cells.