Studies of "pinwheel-like" bis[1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninato] rare earth(III) double-decker complexes
Author(s)
Wang, Rongming
Li, Renjie
Bian, Yongzhong
Choi, Chi-Fung
K. P. Ng, Dennis
Dou, Jianmin
Wang, Daqi
Zhu, Peihua
Ma, Changqin
D. Hartnell, Regan
P. Arnold, Dennis
Jiang, Jianzhuang
Griffith University Author(s)
Year published
2005
Metadata
Show full item recordAbstract
Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [M-III{Pc(alpha-OC5H11)(4)}(2)] (M=Eu, Y, Lu; Pc(alpha-OC5H11)(4)=1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(alpha-OC5H11)(4) with the corresponding M(acac)(3)(.)nH(2)O (acac = acetylacetonate) in refluxing n-octanol. Due to the C-4h symmetry of the Pc(alpha-OC5H11)(4) ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C-4h and D-4 symmetry. The former isomer, which is a major product, can be partially separated by recrystallization due ...
View more >Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [M-III{Pc(alpha-OC5H11)(4)}(2)] (M=Eu, Y, Lu; Pc(alpha-OC5H11)(4)=1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(alpha-OC5H11)(4) with the corresponding M(acac)(3)(.)nH(2)O (acac = acetylacetonate) in refluxing n-octanol. Due to the C-4h symmetry of the Pc(alpha-OC5H11)(4) ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C-4h and D-4 symmetry. The former isomer, which is a major product, can be partially separated by recrystallization due to its higher crystallinity. The molecular structure of the major isomer of the Y analogue has been determined by single-crystal Xray diffraction analysis. The metal center is eight-coordinate bound to the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Such an arrangement leads to an interesting "pinwheel" structure when viewed along the C-4 axis, which assumes a very unusual S-8 symmetry The major isomers of all these double-deckers have also been characterized with a wide range of spectroscopic methods. A systematic investigation of their electronic absorption and electrochemical data reveals that the pi-pi interaction between the two Pc(alpha-OC5H11)(4) rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalo-cyaninato) analogues.
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View more >Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [M-III{Pc(alpha-OC5H11)(4)}(2)] (M=Eu, Y, Lu; Pc(alpha-OC5H11)(4)=1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(alpha-OC5H11)(4) with the corresponding M(acac)(3)(.)nH(2)O (acac = acetylacetonate) in refluxing n-octanol. Due to the C-4h symmetry of the Pc(alpha-OC5H11)(4) ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C-4h and D-4 symmetry. The former isomer, which is a major product, can be partially separated by recrystallization due to its higher crystallinity. The molecular structure of the major isomer of the Y analogue has been determined by single-crystal Xray diffraction analysis. The metal center is eight-coordinate bound to the isoindole nitrogen atoms of the two phthalocyaninato ligands, forming a distorted square antiprism. Such an arrangement leads to an interesting "pinwheel" structure when viewed along the C-4 axis, which assumes a very unusual S-8 symmetry The major isomers of all these double-deckers have also been characterized with a wide range of spectroscopic methods. A systematic investigation of their electronic absorption and electrochemical data reveals that the pi-pi interaction between the two Pc(alpha-OC5H11)(4) rings is weaker than that for the corresponding unsubstituted or beta-substituted bis(phthalo-cyaninato) analogues.
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Journal Title
Chemistry: A European Journal
Volume
11
Subject
Chemical Sciences