Synthesis Of Benzothieno[60]fullerenes Through Fullerenyl Cation Intermediates

Fullerene cation chemistry is different from fullerene anion and fullerene radical chemistry.Fullerene cation chemistry show their advantages which is high yields,short reaction time,high chemo-selectivity and unique products'structures,Fullerene cation intermediates provide a new strategy for the synthesis of various fullerene derivatives.This dissertation will systematically introduce the synthesis of fullerene heterocyclic compound through fullerene cation chemistry.Benzothieno[60]fullerenes were synthesized using fullerenyl cations as key intermediates.The reaction proceeded through a nucleophilic attack of the sulfur atom as a weak nucleophile to the fullerenyl cation electrophile.A monoarylated fullerene,(2-methylthiophenyl)hydro[60]fullerene,C60ArH(Ar=C6H4-SMe-2,and so on;four derivatives)was subjected to deprotonation with KOtBu to form a fullerenyl anion ArC60-,followed by oxidation using I2 to generate a fullerenyl cation ArC60+leading to intramolecular demethylative cyclization via fullerene cation-S interaction to the product.Electrochemical and computational studies revealed slightly narrower band gap of this compound than usual fullerene derivatives because of the relatively high-lying HOMO of the fused thieno moiety.In conclusion,the mechanism of the intramolecular cyclization will be integrally studied,it's helpful to guide the synthesis of heterocyclic fullerene derivatives that can be used in solar cells,which benefit the application of Polymer solar cells in the future.