Optically Active Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Triple-Decker Complexes. Synthesis, Spectroscopy, and Effective Chiral Information Transfer

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• 作者：Jitao Lu ; Yanhua Deng ; Xiaomei Zhang ; Nagao Kobayashi ; Jianzhuang Jiang
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：March 21, 2011
• 年：2011
• 卷：50
• 期：6
• 页码：2562-2567
• 全文大小：883K
• 年卷期：v.50,no.6(March 21, 2011)
• ISSN：1520-510X

文摘

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 [M₂(Pc)₂(TCBP)] {TCBP = Meso-tetrakis [3,4-(11,12:13,14-di(1鈥?2鈥?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)-H₂TCBP with M(Pc)₂ in the presence of corresponding M(acac)₃路nH₂O (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, ¹H 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 蟺鈭捪€ interaction between porphyrin and phthalocyanine rings. In addition, their electrochemical properties have also been investigated by cyclic voltammetry (CV).