高等学校化学学报 ›› 2006, Vol. 27 ›› Issue (2): 244.

• 研究论文 • 上一篇    下一篇

[60]富勒烯硫桥键联1,3-二硫杂环戊烯基-2-硫酮衍生物的理论研究及合成和表征

吕梅香2, 曾和平1,2   

  1. 1. 华南理工大学化学院功能分子研究所, 广州 510641; 2. 华南师范大学化学学院, 广州 510631
  • 收稿日期:2005-01-18 出版日期:2006-02-10 发布日期:2006-02-10
  • 通讯作者: 曾和平(1955年出生), 男, 博士, 教授, 博士生导师, 主要从事富勒烯功能化材料的研究. E-mail: zenghp@scnu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20231020, 20471020)和广东省自然科学基金(批准号: 36585)资助

Theoretical Study, Synthesis and Characterization of the [60] Fullerene
Sulfurbridge Linked 2-Thioxo-1,3-dithioles Derivatives

LU Mei-Xiang2, ZENG He-Ping 1,2   

  1. 1. Institute of Functional Molecule, Faculty of Chemistry, South China University of Technology,
    Guangzhou 510641, China;
    2. College of Chemistry, South China Normal University, Guangzhou 510631, China
  • Received:2005-01-18 Online:2006-02-10 Published:2006-02-10
  • Contact: ZENG He-Ping ,E-mail: zenghp@scnu.edu.cn

摘要:

摘要为了获得具有长寿命电荷分离态的[60]富勒烯-富硫衍生物有机功能分子, 我们设计了用单键硫桥键联[60]富勒烯和硫酮衍生物的分子7和8, 用半经验AM1方法得出最低能量的几何结构, 在此基础上用密度泛函(DFT) B3LYP/3-21G方法,对其进行计算, 得出电子相关的优化参数, 预测其稳定性. 发现用硫桥链接后, 硫酮部分和C60部分之间的距离比文献报道的无硫桥链接的C60衍生物要短, 且能隙变小, 使得在光激发下形成激发态较容易. 同时用硫酮烯砜6与C60发生Diels-Alder环加成反应, 合成了这两个新化合物, 用TOF-MS, 1H NMR, 13C NMR, IR, UV-Vis和荧光光谱等进行了结构表征.

关键词: 60衍生物; 优化参数; 合成; 结构表征

Abstract:

Abstract To attaining longlived charge separated states, the new compounds 7 and 8 of C60-S-2-thioxo-1,3-dithioles derivatives were synthesized by Diels-Alder cycloaddition reaction. The structures generated by AM1 were used as the initial configurations for the density functional optimization(DFT)at the B3LYP/3-21G level for all carbon and sulfur clusters, and some geometry conformation indexes were obtained. We found that C60 has been halfpacked by the curved 2-thioxo-1,3-dithioles derivatives. The distant space between donor and acceptor is shorter than no sulfur-bridge covalent bond linked and the energy gap is smaller. A longlived charge separated states may occur in the [60]fullerene sulfur-bridge covalent bond linked tetrathiafulvalene derivatives when it is excited. The medial and final molecular structures were identified and characterized by TOF-MS, 1H NMR, 13C NMR, FTIR, UV-Vis and Fluorescence spectra.

Key words: C60 derivatives; Optimizing parameter; Synthesis; Structure characterization

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