Functionalization of [60] Fullerene Cations Promoted by Cu Salts

Author:Yang Xiao Yu

Supervisor:song wei zuo yutaka matsuo


Degree Year:2019





Fullerene cation chemistry is different from traditional fullerene chemistry such as fullerene anion and fullerene radical chemistry.Fullerene cation intermediates show their superiors in the synthesis of versatile fullerene derivatives because of high chemo-selectivity,high yields,short reaction time and unique products’structures.This dissertation will not only conduct a systematical development and research on the synthesis of fullerene derivatives based on fullerene cation-mediated processes,but also deeply investigate the performance of fullerene derivatives-engaged perovskite solar cells(PSCs).The fullerene cation intermediates can be fulfilled by starting from the synthesis of hydro fullerene precursors and consequent oxidation of fullerene dimers through step-by-step oxidation process or one-step instant oxidation.Through the investigation on the substrate scope of nucleophilic substrates,the mechanism and the reaction scope can be systematically and deeply unveiled.In addition,the different cyclo[60]fullerene derivatives can be produced through the intramolecular cyclization of fullerene cation intermediates,which were generated from precursors of different aliphatic chain length.Similarly,the mechanism of the intramolecular cyclization will be systematically investigated,which is aimed at guiding the synthesis of cyclo[60]fullerenes that can be applied in SCs.Meanwhile,the performance of fullerene derivatives-engaged PSCs will be investigated by doping methodology.Furthermore,the fullerene derivatives are supposed to be modified and improved according to the performance of PSCs,which broaden the potential application of PSCs in future horizon.The summary research results are as follows:1.Aryl[60]fullerenyl cations(ArC60+)were reacted with various functionalized aryl boronic acids to produce functionalized 1,4-diaryl[60]fullerenes by intermolecular coupling reaction using Cu(II)salts(Cu(BF4)2(aq)).This protocol tolerated various functional groups,such as OH,NH2,COCH3,and Cl substituents,with yields reaching 93%.C60Ar1Ar2(Ar2=p-NH2C6H4)was used as a dopant in a photoactive CH3NH3PbI3 layer of a perovskite solar cell.2.The methodology with in-situ fullerene-cation-mediated intramolecular cyclization provided high selectivity and efficient access to six-membered tetrahydronaphthaleno[60]fullerenes with remarkable functional group tolerance and excellent yields by CuBr2.Furthermore,high solubilities of tetrahydronaphthaleno[60]fullerenes were reported.3.A fullerene-cation-mediated synthesis,accessing a new class of 5-membered-carbon-ring cyclo[60]fullerenes with high yields of up to 93%was showcased.This method utilized aryl[60]fullerene cations,ArC60+as intermediates,which were generated in situ by heating the aryl[60]fullerenyl dimers in the presence of CuBr2.In addition,5-membered-carbon-ring cyclo[60]fullerenes displayed excellent device applicability.