N-甲基-2-(4'-N-乙基咔唑基)-[60]富勒烯吡咯烷及其衍生物的合成, 电荷分离态特征

通过1,3-偶极环加成方法在微波照射下合成了N-甲基-2-(4'-N-乙基咔唑基)-富勒烯吡咯烷(C₆₀-Cz)和N-甲基-2- (4'-N,N-二苯基氨基)-富勒烯吡咯烷(C₆₀-TPA), 用质谱, ¹H NMR, IR等对其结构进行了表征. 用激光光解时间分辨瞬态谱研究了N-甲基-2-(4'-N-乙基咔唑基)-富勒烯吡咯烷的分子内电荷转移过程, 在近红外区观测到了长寿命电荷分离态C₆₀^•--C_Z^•+的存在, 其寿命为0.28 μs. 运用Gaussian 98量子化学程序包, 利用密度泛函的方法对N-甲基-2-(4'-N,N-二苯基氨基)-富勒烯吡咯烷几何构型进行了优化, 并在优化基础上用ZINDO方法计算了化合物C₆₀-TPA的电子光谱, 计算结果表明, 光谱吸收峰在440 nm, 与实验值433 nm基本一致.

Synthesis, Charge-separated State Characterization of N-Methyl-2-(4''-N-ethylcarbozole)-3-fulleropyrrolidine and Its Drivatives

N-Methyl-2-(N-ethylcarbozole)-fulleropyrrolidine and N-methyl-2-(4'-N,N-diphenylamino)-full- eropyrrolidine were synthesized by 1,3-dipolar cycloaddition under microwave irradiation, which were characterized by MS, ¹H NMR, IR and UV-Vis. Photoinduced intramolecular electron transfer process from C₆₀ moiety to carbazole moiety has been studied by nanosecond laser flash photolysis. The charge-separated state C₆₀^•--C_Z^•+ was observed in the near-IR region with its life of 0.28 μs. The electronic spectrum of the C₆₀-TPA was studied by using ZINDO method on the basis of the optimized geometrics with B3LYP/6-31G* program. The results showed that the calculated absorption was beyond 440 nm, essentially consistent with experimental value 433 nm.