Ferrocene-phenothiazine conjugated molecules : Synthesis, structural characterization, electronic properties, and DFT-TDDFT computational study
Ferrocene-phenothiazine conjugated molecules : Synthesis, structural characterization, electronic properties, and DFT-TDDFT computational study
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DOI：
10.1021/om060923o
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发表时间：
2007-02
期刊：
影响因子：
2.8
通讯作者：
Wenwei Zhang;Yong Yu;Zhengyu Lu;Wei Mao;Yi-zhi Li;Q. Meng
中科院分区：
文献类型：
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作者：
Wenwei Zhang;Yong Yu;Zhengyu Lu;Wei Mao;Yi-zhi Li;Q. Meng
通过Sonogashira交叉偶联反应合成了两个新的Fc-MPT共轭化合物3-（二茂铁乙炔基）-10-甲基吩噻嗪（1）和3，7-双（二茂铁乙炔基）-10-甲基吩噻嗪（2）。单晶X-射线衍射表明，2显示出更好的共面性之间的Fc和MPT亚基。晶体堆积表明，1通过（Fc部分的）S. H-C氢键在相邻分子之间以相同的方向堆叠，而2在相邻分子之间以相反的方式堆叠，不仅通过（MPT部分的）S. H-C氢键，而且通过π. π相互作用。两种配合物在溶液中均表现出MLCT、ICT和n → π* 跃迁，其中2具有明显的红移，并表现出较高的振子强度，这一点已被TDDFT理论计算所证实. DFT计算解释了这两种配合物的电化学性质，并表明2中较大的共轭效应导致较小的HOMO-LUMO能隙（Eg）。1和2之间的差异表明，结构和共轭效应对分子的电子性质有很大的影响。
Two novel Fc-MPT conjugated compounds, 3-(ferrocenylethynyl)-10-methylphenothiazine (1) and 3,7-bis(ferrocenylethynyl)-10-methylphenothiazine (2), have been synthesized by Sonogashira cross-coupling reactions. Single-crystal X-ray diffraction shows that 2 displays better coplanarity between the Fc and MPT subunits. The crystal packing reveals that 1 stacks in the same direction between the neighboring molecules by the S…H-C (of the Fc moiety) hydrogen bonds, while 2 stacks in an inverse fashion between the adjacent molecules, not only by the S…H-C (of the MPT moiety) hydrogen bonds but also by π…π interactions. Both complexes show MLCT, ICT, and n → π* transitions in the UV-visible range in solution, and 2 has a tremendous bathochromic shift and shows a higher oscillator strength of the absorption, which has been verified by TDDFT theoretical calculations. DFT calculations explain the electrochemistry of the two complexes and show that the larger conjugative effect in 2 leads to the smaller HOMO-LUMO gap (Eg). The differences between 1 and 2 indicate that the structural and conjugative effects have great influence on the electronic properties of the molecules.