高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (4): 952.doi: 10.7503/cjcu20120694

• 物理化学 • 上一篇    下一篇

新型π-扩展TTF衍生物的合成、晶体结构及量子化学计算

朱玉兰1,2, 曹丽1,2, 马奎蓉1, 田礼彬1, 王新龙2, 苏忠民2   

  1. 1. 淮阴师范学院化学化工学院, 江苏省低维材料化学重点建设实验室, 淮安 223300;
    2. 东北师范大学化学学院, 长春 130024
  • 收稿日期:2012-07-24 出版日期:2013-04-10 发布日期:2013-03-15
  • 通讯作者: 朱玉兰,女,教授,主要从事有机功能分子材料研究.E-mail:ylzhu1998@126.com E-mail:ylzhu1998@126.com
  • 基金资助:

    国家自然科学基金(批准号:20671038)和江苏省低维材料化学重点建设实验室开放课题(批准号:JSKC11098)资助.

Synthesis, Crystal Structure and Quantum-chemical Calculation of Novel π-Extended Tetrathiafulvalene Derivatives

ZHU Yu-Lan1,2, CAO Li1,2, MA Kui-Rong1, TIAN Li-Bin1, WANG Xin-Long2, SU Zhong-Min2   

  1. 1. Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, China;
    2. Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2012-07-24 Online:2013-04-10 Published:2013-03-15

摘要:

以对苯二胺为起始原料合成了2个新型的π-扩展四硫富瓦烯(TTF)衍生物, 即N,N'-2(4,5-二苄硫基-1,3-二硫杂环戊烯-2-叶立德)-苯-1,4-二胺(5a)和N,N'-2(4,5-二甲酯基-1,3-二硫杂环戊烯-2-叶立德)-苯-1,4-二胺 (5b), 并利用氢核磁共振(1H NMR)、 质谱(MS)、 傅里叶变换红外光谱(FTIR)和单晶X射线衍射(XRD)等方法对化合物结构进行了表征. 晶体结构分析结果表明, 化合物5a和5b分属三斜晶系、 P1空间群和单斜晶系、 P21/n空间群. 化合物5a和5b均为非平面结构分子, 分子中对苯二亚胺平面和1,3-二硫杂环平面形成的二面角分别为 87.61°(5a)和43.77°(5b). 运用 Gaussian 09程序, 采用密度泛函理论(DFT)方法在 B3LYP/6-31+G(d,p)水平上进行了量子化学计算, 对化合物的前线分子轨道、 静电势和电子吸收光谱进行了讨论, 计算结果与实验值基本一致.

关键词: 四硫富瓦烯, 晶体结构, 密度泛函理论

Abstract:

Two novel π-extended tetrathiafulvalene derivatives, N,N'-bisbenzene-1,4-diamine(5a) and N,N'-bisbenzene-\{1,4-diamine(5b) were synthesized with p-phenylenediamine as starting material. The molecular structures were identified and characterized by 1H NMR, mass spectrometry(MS), Fourier transform infrared(FTIR) and single-crystal X-ray diffraction(XRD). Crystal structure analysis shows that compounds 5a and 5b belong to triclinic and monoclinic system, with space group P1 and P21/n, respectively. The planes of the bis(imino)benzene in compounds 5a and 5b twisted from the plane of the two dithiole rings with a dihedral angle of 87.61° for compound 5a, and 43.77° for compound 5b, respectively. Moreover, the density functional theory(DFT) calculations are also carried out with Gaussian 09 program at the B3LYP/6-31+G(d,p) level to investigate the frontier orbital, electrostatic potential and spectroscopy. The experimental results are generally in good agreement with those obtained from DFT calculations.

Key words: Tetrathiafulvalene, Crystal structure, Density functional theory

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