新型π-扩展TTF衍生物的合成、晶体结构及量子化学计算

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.

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

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.