The facile one-step reaction of [60]fullerene with primary amides promoted by cheap and easily available ferric perchlorate afforded a series of interesting fullerooxazole derivatives. The reaction was tolerant of a large variety of primary amides containing aryl, alkyl, and cinnamyl groups. A possible reaction mechanism for product formation was proposed.

•The covalently linked POM/zinc(II) porphyrin hybrid was synthesized and characterized.•There is a strong delocalisation and charge transfer between POM and the grafted zinc porphyrin segments in the hybrid.•The hybrid displayed interesting electrical conductivity behavior and photovoltage response.A novel covalently-linked organic-polyoxometalate (POM) hybrid compound [NBu4]6[α2-P2W17O61{P(O)Porp}2] (DM) (Porp = Zn(II)-5-(4-phenyl),10,15,20-triphenylporphyrin) was prepared by treating Dawson-type K10[α2-P2W17O61] (D) with Zn(II)-5-[4-(dihydroxyphosphoryl)phenyl],10,15,20-triphenylporphyrin (M), and characterized by NMR, IR, UV–vis, fluorescence spectra and cyclic voltammetry. The study on photophysical properties displayed that there is a strong delocalisation and charge transfer between D and the grafted zinc porphyrin segments in the hybrid compound DM. The redox potential of the polyanion can be tuned by the grafting zinc porphyrin segments on it. The DM displayed interesting electrical conductivity behavior and photovoltage response.A novel covalently-linked organic-polyoxometalate (POM) hybrid compound [NBu]4]6[α2-P2W17O61{P(O)Porp}2] (DM) (Porp = Zn(II)-5-(4-phenyl),10,15,20-triphenylporphyrin) was prepared by treating Dawson-type K10[α2-P2W17O61] (D) with Zn(II)-5-[4-(dihydroxyphosphoryl)phenyl],10,15,20-triphenylporphyrin (M). The DM displayed interesting electrical conductivity behavior and photovoltage response.

The facile one-step reaction of [60]fullerene with aldehydes and primary amines in the presence of cheap and easily available Cu(OAc)2·H2O afforded a series of new types of fulleropyrrolines with trisubstituted C═C bonds in good to excellent yields, which would be difficult to prepare by known methods. The formed fulleropyrroline under the assistance of Pd(OAc)2 and CuCl2·2H2O could be further converted to 1-fulleropyrrolidine by the chlorohydroxylation reaction of C═C bond. Subsequent elimination reaction of 1-fulleropyrrolidine with the aid of TsOH·H2O generated the scarce 1-fulleropyrroline derivative.

A series of scarce N-unsubstituted 2,5-diaryl fulleropyrrolidines as cis isomers could be prepared via the facile one-step reaction of [60]fullerene with N-unsubstituted arylmethanamines promoted by cheap and easily available ferric perchlorate. Nevertheless, the reaction of N-substituted arylmethanamines with [60]fullerene under the same conditions gave different experimental results. N-Methylbenzylamine formed N-methyl 2,5-diphenyl fulleropyrrolidine as a trans isomer, and N,N-dibenzylamine unexpectedly afforded the N-unsubstituted 2,5-diphenyl fulleropyrrolidine as a cis isomer. Intriguingly, high stereoselectivity for all 2,5-diaryl fulleropyrrolidines could be observed although both cis and trans isomers were possibly formed. N-Unsubstituted fulleropyrrolidine could be further converted to N-substituted fulleropyrrolidines under the assistance of an acid chloride or an isocyanate. A possible reaction pathway leading to 2,5-diaryl fulleropyrrolidines is also proposed.

Thermal reaction of [60]fullerene with various arylmethanamines in the presence of aromatic aldehydes under air conditions afforded a series of rare 2,5-diaryl fulleropyrrolidines. Intriguingly, the obtained fulleropyrrolidines exhibited different stereoselectivity. N-unsubstituted arylmethanamines exclusively produced 2,5-diaryl fulleropyrrolidines as cis isomers, while N-substituted arylmethanamines with rare exceptions always gave 2,5-diaryl fulleropyrrolidines as trans isomers. Theoretical calculations at the level of B3LYP/6-31G (d,p) were employed to elucidate the stereoselectivity of N-substituted 2,5-diaryl fulleropyrrolidines as trans isomers by investigating the transition-state structures of different cycloaddition pathways.

The double nucleophilic substitution reaction of aziridinofullerene with diols in the presence of p-toluenesulfonic acid affords a series of rare fullerene-fused dioxygenated ring compounds with six- to ten-membered heterocycles. A possible reaction mechanism for product formation is proposed.

The facile one-step reaction of [60]fullerene with various diols in the presence of ferric perchlorate afforded a series of rare fullerene-fused dioxanes/dioxepanes. Nevertheless, the reaction of [60]fullerene with diethylene glycol, triethylene glycol, and tripropylene glycol promoted by ferric perchlorate unexpectedly generated fullerene-fused dioxanes instead of the anticipated fullerene-fused crown ethers. A plausible reaction mechanism is proposed to explain the formation of fullerene-fused dioxane/dioxepane products.