Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
Inorg Chem. 2011 Mar 21;50(6):2562-7. doi: 10.1021/ic102393c. Epub 2011 Feb 4.
With the view to creating novel sandwich-type tetrapyrrole rare earth complexes toward potential applications in material science and chiral catalysis, two new optically active mixed (phthalocyaninato)(porphyrinato) rare earth triple-decker complexes with both (R)- and (S)-enantiomers [M(2)(Pc)(2)(TCBP)] {TCBP = Meso-tetrakis [3,4-(11,12:13,14-di(1',2'-naphtho)-1,4,7,10,15,18-hexaoxacycloeicosa-2,11,13-triene)-phenyl] porphyrinate; M = Eu (1), Y (2)} have been designed and prepared by treating optically active metal free porphyrin (R)-/(S)-H(2)TCBP with M(Pc)(2) in the presence of corresponding M(acac)(3)·nH(2)O (acac = acetylacetonate) in refluxing 1,2,4-trichlorobenzene (TCB). These novel mixed ring rare earth triple-decker compounds were characterized by a wide range of spectroscopic methods including MS, (1)H NMR, IR, electronic absorption, and magnetic circular-dichroism (MCD) spectroscopic measurements in addition to elemental analysis. Perfect mirror image relationship was observed in the Soret and Q absorption regions in the circular-dichroism (CD) spectra of the (R)- and (S)-enantiomers, indicating the optically active nature of these two mixed (phthalocyaninato)(porphyrinato) rare earth triple-decker complexes. This result reveals the effective chiral information transfer from the peripheral chiral binaphthyl units to the porphyrin and phthalocyanine chromophores in the triple-decker molecule because of the intense π-π interaction between porphyrin and phthalocyanine rings. In addition, their electrochemical properties have also been investigated by cyclic voltammetry (CV).
为了创造新型夹心型四吡咯稀土配合物，以应用于材料科学和手性催化领域，我们设计并制备了两个新型光学活性的混合（酞菁基）（卟啉基）稀土三明治型三重堆积配合物，它们具有（R）-和（S）-对映异构体[M(2)(Pc)(2)(TCBP)]{TCBP = Meso-四[3,4-(11,12:13,14-二(1',2'-萘基)-1,4,7,10,15,18-六氧杂环二十烷-2,11,13-三烯基)]卟啉基; M = Eu(1), Y(2)}。通过在回流的 1,2,4-三氯苯(TCB)中，用 M(Pc)(2)处理光学活性的金属卟啉（R）-/(S)-H(2)TCBP，同时加入相应的 M(acac)(3)·nH(2)O(acac = 乙酰丙酮酸盐)，制备了这两种新型的混合环稀土三重堆积化合物。这些新型混合环稀土三重堆积化合物通过多种光谱方法进行了表征，包括 MS、(1)H NMR、IR、电子吸收和磁圆二色性(MCD)光谱测量，以及元素分析。在圆二色性(CD)光谱的 Soret 和 Q 吸收区域中观察到了（R）-和（S）-对映异构体之间的完美镜像关系，表明这两种混合（酞菁基）（卟啉基）稀土三重堆积配合物具有光学活性。这一结果表明，由于卟啉和酞菁环之间的强烈π-π相互作用，外围手性联萘单元有效地将手性信息传递给三重堆积分子中的卟啉和酞菁发色团。此外，我们还通过循环伏安法(CV)研究了它们的电化学性质。
