The Electrochemical Functionalizations of [60] Fullerene and Its Derivatives

Author:Liu Kai Qing

Supervisor:wang guan wu


Degree Year:2019





Fullerenes are considered as an important part of carbon allotropes.Considerable efforts have been made to synthesize various fullerene derivatives by chemists.These functionalized fullerene derivatives show great potential applications in materials science,biomedicine,and nanoscience.Recently,electrochemical synthesis of fullerene derivatives become more and more popular owing to its mild reaction conditions,high efficiency and regioselectivity.In this dissertation,the main work is focused on the synthesis of fullerene derivatives with novel addition patterns by electrochemical methods.The obtained selectivity is rationalized by theoretical calculations.1.A series of carbocyclic[60]fullerene derivatives were synthesized by the reactions of electrochemical generated C602-with dibromide reagents.The ratio of stereoisomers was rationalized by theoretical calculations.It provides a new and efficient method to construct carbocyclic[60]fullerene derivatives.2.Three different types of fullerene derivatives were synthesized by the reactions of electrochemical generated C602-with bulky electrophiles.When C602-was reacted with diphenylmethyl bromide,a 1,2-or l,4-adduct could be generated.When C602-was reacted with BrCH(CO2Et)2,a methanofullerene product would be obtained.When C602-was reacted with BrCPh3,the C120 dimer was produced.The studies of these reactions give a better understanding of the reaction behaviors between C602-and bulky electrophiles.3.Tetraadduct fullerene derivatives with a novel 1,2,4,17-addition pattern or 1,2,3,4-addiction pattern were synthesized by the reaction of[60]fullroindoline dianions with 1,2-bis(bromomethyl)benzene.The obtained 1,2,4,17-adduct could be further electrochemically functionalized with trifluoacetic acid to generate 1,2,3,4,9,10-hexaadduct.The obtained 1,2,4,17-addition pattern was first reported in the fullerene chemistry.The method for synthesizing fullerene derivatives with multi-addition pattern by electrochemical method provides an idea for designing and synthesizing a novel addition mode fullerene derivative in the future.4.An unexpected fullerene derivative with 1,2,3,4-addition pattern was synthesized by the reaction of electrochemically generated[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)dianion with diiodomethane.The electrochemical and organic solar cell properties of the obtained product were preliminarily investigated.