The Synthesis, Characterization, And Nonlinear Optical Properties Of C₆₀ Derivatives Of Acetylene Substituted By Pyrimidine

The discovery of C60 raised a lot of interets because of some specific physicochemical properties. Exceptionally large nonlinear optical (NLO) response in C60 had been reported, and diacetylene complexes have the large NLO suspceptibilities, so the novel idea of introducing diacetylene to C60 to improve the NLO suspceptibilities was supposed. Based on above analysis, a series of novel pentadiynes substituted with pyrimidinyl group were synthesised, and the reaction between them and C60 was applied to synthesize fullerene derivatives of diacetylene substituted by pyrimidine groups. Following are the abstract of our study work:1. The chemical property of C60 and characterization of C60 derivatives via 13C NMR spectroscopy were summarized at first, and the recent progresses in the nonlinear optical C60 derivatives were reviewed.2. 5-(2-methylthio-4-methyl-5-pyrimidinyl)-2,4-pentadiyne-1-ol sorbate (SPD) was synthesized, which was confirmed by IR, 1H NMR, 13C NMR, DEPT, gCOSY, gHSQC and gHMBC spectra. Its cyclization reaction was studied.3. According to our experiments, appropriate conditions for the reaction of C60 with SPD were obtained. There will be less byreactions at 125℃ for 12~16 hours under nitrogen in the dark.4. Three C60 derivatives were observed in this reaction: C60SPD1, C60SPD2, C60SPD3, and the products were obtained by column chromatography on silica gel.5. C60SPD2 was characterized by MS, UV-vis, IR, 1H NMR, 13C NMR, DEPT, gCOSY, gHSQC and gHMBC spectra, and two reaction mechanisms of were proposed.6. Aza-bridged C60 derivative (C60NPD) was synthesized, which was characterized by MALDI-TOF-MS and UV-vis spectra.7. The optical nonlinear properties of these C60 derivatives were measured using a Q-switched Nd:YAG laser with 8 ns pulse excitation at 532 nm. The reverse saturation absorption and nonlinear refraction of C60NPD were observed by means of Z-scan technique and the value of third-order optical nonlinear susceptibilitie χ(3) was obtained. The optical limiting properties of these C60 derivatives were also studied and results show that C60NPD has a good optical limiting performance.