Study On The Reaction Of [60]Fullerene With Arylaldehydes And Amines Promoted By Magnesium Perchlorate

Chemical modification is one of the most important research fields in the fullerene chemistry.Many fullerene derivatives have been synthesized over the past decades.The introduction of versatile functional groups and structural units on the fullerene core is useful for modifying its physicochemical properties,including its solubility,intermolecular forces and interface energy,and provides new opportunities to exploit these different properties for expanding their applications in the fields of photoelectric materials,nanomaterials,supramolecular chemistry and biomedicine.In recent years,the reaction to the synthesis of fullerene derivatives with the aid of various metal salts has attracted significant attention.Therefore,the development of new and effective methods for creating scarce and novel fullerene derivatives is of crucial importance.In this thesis,we mainly describe the magnesium perchlorate-mediated reaction of[60]fullerene(C60)with arylaldehydes and amines to afford the scarce 2,5-diaryl fulleropyrrolidine and cyclopentafullerene derivatives,respectively.Various reaction conditions such as reaction time,reaction temperature and reactant ratio have been screened to achieve the best product yields.In addition,all of new compounds have been fully characterized by their HRMS,1H NMR,13C NMR,FT-IR,and UV-vis spectra.Finally,plausible reaction mechanisms for the formation of 2,5-diaryl fulleropyrrolidines and cyclopentafullerenes are also suggested.Chapter I:IntroductionThis chapter introduced the discovery,structure,performance of C60.An overview of recent development of novel fullerene chemical reactions at home and aboard,especially for the addition reactions of C60 promoted by various metal salts,was also provided.In addition,the idea about this research was displayed in this chapter.Chapter II:The synthesis and characterization of 2,5-diaryl fulleropyrrolidinesThe facile one-step reaction of C60 with arylmethanamines and arylaldehydes in the presence of magnesium perchlorate under air conditions generated a series of scarce 2,5-diaryl fulleropyrrolidines in good to excellent yields.Intriguingly,all the formed 2,5-diaryl fulleropyrrolidines were confirmed only as cis isomers and thus displayed high stereoselectivity.In addition,the type of arylaldehyde was found to have a great correlation with the formation of different 2,5-diaryl fulleropyrrolidines.Arylaldehydes without electron-withdrawing groups always afforded exclusively the desired 2,5-diaryl fulleropyrrolidines,while arylaldehydes connecting electron-withdrawing groups unexpectedly produced symmetrical 2,5-diaryl fulleropyrrolidines besides the anticipated fulleropyrrolidines.A plausible formation mechanism for the 2,5-diaryl fulleropyrrolidines was proposed,Chapter?:The synthesis and characterization of cyclopentafullerenesThe magnesium perchlorate-mediated reaction of C60 with aldehydes and triethylamine under air conditions afforded a series of rare cyclopentafullerenes in moderate yields with high stereoselectivity.A plausible reaction mechanism was suggested to elucidate the formation of cyclopentafullerenes.