| Fullerenes have gotten a lot of interests since they were discovered because of their special structure exceptional physical and chemical properties.In this dissertation,the Diels-Alder addition reaction and molecular switch reaction are explored by using fullerenes.The following are the main points:（1）We studied the Diels-Alder addition reaction of three bisanthracene compounds connected with different chain lengths to fullerenes.When using 3He@C60 to react with these three bisanthracene compounds,the addition of bisanthracene compounds to fullerenes can be easily determined according to the 3He NMR signals.It can be found from the spectrum analysis that the long-chain bianthracene compounds can undergo bisaddition reaction with fullerenes at low concentrations,while the short-chain bianthracene compounds can only obtain monoaddition products.And the Diels-Alder addition reaction between 9,10-dimethylanthracene（DMA）and fullerenes was studied using H2@C60.It is determined that the Diels-Alder addition reaction of C60 and DMA can obtain one mono-adduct,six bisadducts,eleven tris-adducts,and ten tetra-adducts,and the equilibrium constant of adducts are calculated;（2）Porphyrin-crown ether compounds were synthesized,and the complexation mode between porphyrin-crown ether and C60 was simulated by density functional theory.The molecular interactions between porphyrin-crown ether and C60 were investigated by UV-vis spectroscopy and steady-state fluorescence spectroscopy,and the multiple responses between porphyrin-crown ether and C60 supramolecular system were also studied.In addition,the supramolecular complexation of porphyrin-crown ether compounds with C60 was studied by 1H NMR using H2@C60 instead of C60,and the nuclear magnetic signal transfer of H2@C60in the supramolecular system was realized for the first time;（3）A novel bisporphyrin Cavitand molecular switch compound was synthesized by modifying the arms of Cavitand.1H NMR test showed that Cavitand could complex C60 and release C60 when adding trifluoroacetic acid.In addition,the mass spectrum signal of Cavitand complex C60 was obtained successfully for the first time,which clearly verified the formation of the supramolecular system of bisporphyrin-fullerenes.The supramolecular interaction between bisporphyrin and fullerenes was analyzed by UV-vis spectroscopy and fluorescence spectroscopy.The results showed that the complexation effect of Cavitand on C70 was stronger than that of C60.The supramolecular complexation of bisporphyrin Cavitand on fullerenes was studied using H2@C60 as a nuclear magnetic probe molecule.The Cavitand molecular switch compound of porphyrin-fullerene with donor and acceptor units was successfully prepared from cavitand compound through7-step reactions.The molecular weight of Cavitand was up to 3062.99.The1H NMR,13C NMR and MALDI high resolution mass spectrometry of the compound indicated that the target product was successfully synthesized.Subsequent studies will be carried out on the switching properties of the compounds and the electron transfer between intramolecular porphyrins and fullerene groups. |
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