Most of the known open-cage fullerene derivatives contain carbonyl and other relatively inert groups on the rim of the orifice.It is difficult to rationally design further reactions and attach other functional groups ...Most of the known open-cage fullerene derivatives contain carbonyl and other relatively inert groups on the rim of the orifice.It is difficult to rationally design further reactions and attach other functional groups on to these open-cage derivatives.In the present work,two molecules of difunctional 1,4-benzenediamine have been incorporated into the rim of an open-cage C60 derivative through one amino group leaving the other amino group free for further functionalization.The difunctional 4-aminophenol reacted analogously to form an open-cage derivative with a free OH group each on the two phenyl rings.The amino and hydroxyl groups on the phenyl ring above the rim of the orifice showed similar reactivity as aniline and phenol.One of the carbonyl groups on the rim of the orifice could be selectively reduced by NaBH4 and P(OEt)3.The reduction reactions were reversible and the reduced products could be readily converted back to the carbonyl precursor.Thus,this redox process acts as a tool to fine tune the size of the orifice for host-guest studies.展开更多
Functional groups on the rim of open-cage fullerenes usually exhibit different reactivity from those in classical organic molecules due to the unique spherical structure of fullerenes.The present work shows a sequence...Functional groups on the rim of open-cage fullerenes usually exhibit different reactivity from those in classical organic molecules due to the unique spherical structure of fullerenes.The present work shows a sequence of lactone opening,imino hydrolysis,aminal formation and imine formation processes during the reaction of aniline with the open-cage compound 1 with functional groups including lactone on the rim of the orifice.Single crystal X-ray diffraction analysis confirmed the structure of the product.展开更多
Open-cage fullerenes with carbonyl functional groups on the rim of the orifice are ideal precursors for the extension of fullerene π-systems.Unlike isopropylphenylaniline,which reacts selectively with the lactone moi...Open-cage fullerenes with carbonyl functional groups on the rim of the orifice are ideal precursors for the extension of fullerene π-systems.Unlike isopropylphenylaniline,which reacts selectively with the lactone moiety on the rim of the orifice,phenylenediamine reacts with the adjacent carbonyl and imino groups on a pentagon to form a quinoxaline moiety.Further dehydroxylative aromatization connects the fullerene cage π-system with the quinoxaline π-system.Both the NMR and UV-Vis spectra revealed an evident effect after the extension of the fullerene cage π-system.展开更多
基金supported by Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201904)NNSFC(Grant 21871015,22171009,22003003,21901132 and 22261039).
文摘Most of the known open-cage fullerene derivatives contain carbonyl and other relatively inert groups on the rim of the orifice.It is difficult to rationally design further reactions and attach other functional groups on to these open-cage derivatives.In the present work,two molecules of difunctional 1,4-benzenediamine have been incorporated into the rim of an open-cage C60 derivative through one amino group leaving the other amino group free for further functionalization.The difunctional 4-aminophenol reacted analogously to form an open-cage derivative with a free OH group each on the two phenyl rings.The amino and hydroxyl groups on the phenyl ring above the rim of the orifice showed similar reactivity as aniline and phenol.One of the carbonyl groups on the rim of the orifice could be selectively reduced by NaBH4 and P(OEt)3.The reduction reactions were reversible and the reduced products could be readily converted back to the carbonyl precursor.Thus,this redox process acts as a tool to fine tune the size of the orifice for host-guest studies.
基金the National Natural Science Foundation of China(Nos.21272013 and 21132007)the Major State Basic Research Development Program(No.2011CB808401).
文摘Functional groups on the rim of open-cage fullerenes usually exhibit different reactivity from those in classical organic molecules due to the unique spherical structure of fullerenes.The present work shows a sequence of lactone opening,imino hydrolysis,aminal formation and imine formation processes during the reaction of aniline with the open-cage compound 1 with functional groups including lactone on the rim of the orifice.Single crystal X-ray diffraction analysis confirmed the structure of the product.
基金supported by Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201904)NNSFC(Grant 21871015,22171009 and 22003003)the Beijing Outstanding Young Scientist Program(BJJWZYJH01201910001001).
文摘Open-cage fullerenes with carbonyl functional groups on the rim of the orifice are ideal precursors for the extension of fullerene π-systems.Unlike isopropylphenylaniline,which reacts selectively with the lactone moiety on the rim of the orifice,phenylenediamine reacts with the adjacent carbonyl and imino groups on a pentagon to form a quinoxaline moiety.Further dehydroxylative aromatization connects the fullerene cage π-system with the quinoxaline π-system.Both the NMR and UV-Vis spectra revealed an evident effect after the extension of the fullerene cage π-system.
