State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023, People's Republic of China.
J Phys Chem B. 2013 May 2;117(17):5212-21. doi: 10.1021/jp4017757. Epub 2013 Apr 23.
The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.
使用 DFT/TDDFT 方法研究了 6-甲基-5-(9-亚甲基蒽)-(2-丁基脲基-4[1H]-嘧啶酮)(AnUP)对氟阴离子的感应机制。理论结果表明，嘧啶部分的 N3-H3 基团的质子被外加的氟阴离子捕获，然后去质子化。AnUP-二聚体及其去质子化形式的计算垂直激发能与实验结果吻合较好。分子轨道分析表明，AnUP-二聚体的第一激发态(S1)是一个局部激发态，具有π-π*跃迁，而对于去质子化形式，S1 是一个完全的电荷分离态，负责光诱导电子转移(PET)过程。从蒽到嘧啶部分的 PET 过程导致荧光猝灭。
