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Optically Active Mixed Phthalocyaninato–Porphyrinato Rare‐Earth Double‐Decker Complexes: Synthesis, Spectroscopy, and Solvent‐Dependent Molecular Conformations
Author(s) -
Zhang Xiaomei,
Muranaka Atsuya,
Lv Wei,
Zhang Yuexing,
Bian Yongzhong,
Jiang Jianzhuang,
Kobayashi Nagao
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701853
Subject(s) - chemistry , phthalocyanine , crystallography , circular dichroism , tetrapyrrole , protonation , magnetic circular dichroism , metal , molecule , vibrational circular dichroism , double bond , solvent , ring (chemistry) , ligand (biochemistry) , stereochemistry , photochemistry , polymer chemistry , organic chemistry , ion , enzyme , physics , astronomy , spectral line , biochemistry , receptor
Reaction between the optically active metal‐free phthalocyanine with a π system with noncentrosymmetrical C 2v 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.