Optically active mixed phthalocyaninato-porphyrinato rare-earth double-decker complexes: synthesis, spectroscopy, and solvent-dependent molecular conformations.
Reaction between the optically active metal-free phthalocyanine with a pi system with noncentrosymmetrical C(2) [corrected] 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.
Zhang
Xiaomei
X
Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan, China.
Muranaka
Atsuya
A
Lv
Wei
W
Zhang
Yuexing
Y
Bian
Yongzhong
Y
Jiang
Jianzhuang
J
Kobayashi
Nagao
N
D002942:Circular Dichroism; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D008674:Metals, Rare Earth / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D012997:Solvents / Q000737:chemistry
D007211:Indoles; D054833:Isoindoles; D008665:Metalloporphyrins; D008674:Metals, Rare Earth; D012997:Solvents; C013647:phthalocyanine