Chiral bis(phthalocyaninato) yttrium double-decker complexes. Synthesis, structure, spectroscopy, and electrochemistry.
Two new chiral sandwich-type bis(phthalocyaninato) yttrium double-decker complexes including the homoleptic species (R)- and (S)-Y[Pc(OBNP)4]2 (1) and a heteroleptic analogue (R)- and (S)-Y(Pc)[Pc(OBNP)4] (2) {Pc = unsubstituted phthalocyaninate; [Pc(OBNP)4] = tetrakis(dinaphtho[1,2-e:1',2'-g]-1,4-(dioxocine)[2,3-b;2',3'-k;2'',3''-t;2''',3'''-c']phthalocyaninate)} have been synthesized and spectroscopically characterized. In particular, the molecular structures of (R)- and (S)-1 were determined on the basis of single crystal X-ray diffraction analysis, representing the first structurally characterized chiral bis(phthalocyaninato) rare earth double-decker complexes. Perfect mirror-image CD signals observed in the whole phthalocyanine absorption range of the CD spectra of the (R)- and (S)-enantiomers for both compounds reveal the effective chiral information transfer from the peripheral binaphthyl moieties to the phthalocyanine chromophore, while the difference observed in the CD spectrum between 1 and 2 indicates the effect of the chiral substituent number on the chiral information transfer. Nevertheless, the absolute structures unambiguously elucidated for both enantiomers of the homoleptic double-decker render it possible to clarify the chirality of optically active bis(phthalocyaninato) rare earth compounds.
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China. jianzhuang@ustb.edu.cn.
Hang
H
Zhou
Kang
K
Wang
Dongdong
D
Qi
Jianzhuang
J
Jiang
D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques / Q000379:methods*; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism; D015019:Yttrium / Q000737:chemistry*
D007211:Indoles; D054833:Isoindoles; D015019:Yttrium; C013647:phthalocyanine