Zhang Xiaomei, Muranaka Atsuya, Lv Wei, Zhang Yuexing, Bian Yongzhong, Jiang Jianzhuang, Kobayashi Nagao
Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan, China.
Chemistry. 2008;14(15):4667-74. doi: 10.1002/chem.200701853.
Reaction between the optically active metal-free phthalocyanine with a pi system with noncentrosymmetrical C(2) [corrected] symmetry ((S)- and (R)-H(2){Pc(OBNP)(2)}; OBNP=binaphthylphthalocyanine) and half-sandwich complexes [M(III)(acac)(TClPP)] (M=Y, Eu; TClPP=meso-tetrakis(4-chlorophenyl)porphyrinate; acac=acetylacetonate), which were generated in situ from [M(acac)(3)].n H(2)O and H(2)(TClPP) in n-octanol at reflux, provided the first optically active protonated mixed phthalocyaninato-porphyrinato rare-earth double-decker complexes [M(III)H{Pc(OBNP)(2)}(TClPP)] (M=Y, Eu) in good yield. In addition to electronic absorption spectroscopy and magnetic circular dichroism results, circular dichroism shows different spectroscopic features of these mixed-ring rare-earth double-decker compounds in different solvents, such as DMF and CHCl(3), which was well-reproduced on the basis of time-dependent density functional theory calculation results for the yttrium species (S)-Y(III){Pc(OBNP)(2)}(Por) (Por=porphyrinate, which is obtained by removing the four chlorophenyl groups from the TClPP ligand) in terms of the change in the rotation angle between the two macrocyclic ligands in the double-decker molecules. These results revealed the solvent-dependent nature of the molecular conformation of mixed-ring rare-earth double-decker complexes, which suggests a new way of tuning the optical and the electrochemical properties of sandwich-type bis(tetrapyrrole)-metal double-decker complexes in solution by changing the solvent.
具有非中心对称C(2) [已修正] 对称性的含π体系的光学活性无金属酞菁（(S)-和(R)-H(2){Pc(OBNP)(2)}；OBNP = 联萘基酞菁）与半夹心配合物[M(III)(acac)(TClPP)]（M = Y、Eu；TClPP = 中-四(4-氯苯基)卟啉；acac = 乙酰丙酮）之间发生反应，[M(acac)(3)].nH(2)O和H(2)(TClPP)在正辛醇中回流原位生成该半夹心配合物，反应以良好产率得到了首例光学活性质子化混合酞菁基-卟啉基稀土双层配合物[M(III)H{Pc(OBNP)(2)}(TClPP)]（M = Y、Eu）。除电子吸收光谱和磁圆二色性结果外，圆二色性表明这些混合环稀土双层化合物在不同溶剂（如DMF和CHCl(3)）中具有不同的光谱特征，基于钇物种(S)-Y(III){Pc(OBNP)(2)}(Por)（Por = 卟啉，通过从TClPP配体上去除四个氯苯基获得）的含时密度泛函理论计算结果，就双层分子中两个大环配体之间旋转角的变化而言，这一光谱特征得到了很好的重现。这些结果揭示了混合环稀土双层配合物分子构象的溶剂依赖性，这表明通过改变溶剂来调节溶液中夹心型双（四吡咯）-金属双层配合物的光学和电化学性质是一种新方法。
