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Studies of “Pinwheel-Like” Bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] Rare Earth(III) Double-Decker Complexes

By Dennis Arnold, Yongzhong Biang, Chi-Fung Choi, Jianmin Dou, Regan Hartnell, Jianzhuang Jiang, Renjie Li, Changqin Ma, Dennis Ng, Daqi Wang, Rongming Wang and Peihua Zhu


Homoleptic bis(phthalocyaninato) rare-earth double-deckers complexes [MIII{Pc(-OC5H11)4}2] (M=Eu, Y, Lu; Pc(-OC5H11)4=1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate) have been prepared by treating the metal-free phthalocyanine H2Pc(-OC5H11)4 with the corresponding M(acac)3nH2O (acac=acetylacetonate) in refluxing n-octanol. Due to the C4h symmetry of the Pc(-OC5H11)4 ligand and the double-decker structure, all the reactions give a mixture of two stereoisomers with C4h and D4 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 X-ray 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 C4 axis, which assumes a very unusual S8 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 π–π interaction between the two Pc(-OC5H11)4 rings is weaker than that for the corresponding unsubstituted or β-substituted bis(phthalocyaninato) analogues

Topics: 030000 CHEMICAL SCIENCE, Lanthanides, Phthalocyanines, Sandwich Complexes, Structure Elucidation, Yttrium
Publisher: Wiley - V C H Verlag GmbH & Co. KGaA
Year: 2005
DOI identifier: 10.1002/chem.200500214
OAI identifier:
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