Optically active mixed phthalocyaninato-Porphyrinato rare-earth double-decker complexes: Synthesis, spectroscopy, and solvent-dependent molecular conformations

Xiaomei Zhang, Atsuya Muranaka, Wei Lv, Yuexing Zhang, Yongzhong Bian, Jianzhuang Jiang, Nagao Kobayashi

研究成果: Article査読

45 被引用数 (Scopus)

抄録

Reaction between the optically active metal-free phthalocyanine with a π system with noncentrosymmetrical C2v symmetry ((S)- and (R)-H 2{Pc(OBNP)2}; OBNP = binaphthylphthalocyanine) and half-sandwich complexes [MIII(acac)(TClPP)] (M = Y, Eu ; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; acac = acetylacetonate), which were generated in situ from [M(acac)3]·nH2O and H 2(TClPP) in n-octanol at reflux, provided the first optically active protonated mixed phthalocyaninato-porphyrinato rareearth double-decker complexes [MIIIH{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 CHCl3, which was well-reproduced on the basis of time-dependent density functional theory calculation results for the yttrium species (S)-[YIII{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 rareearth 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.

本文言語English
ページ(範囲)4667-4674
ページ数8
ジャーナルChemistry - A European Journal
14
15
DOI
出版ステータスPublished - 2008 5 19

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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