Studies of "pinwheel-like" bis[1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninato] rare earth(III) double-decker complexes

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Title Studies of "pinwheel-like" bis[1,8,15,22-tetrakis(3-pentyloxy)-phthalocyaninato] rare earth(III) double-decker complexes
Author Wang, Rongming; Li, Renjie; Bian, Yongzhong; Choi, Chi-Fung; Ng, Dennis K. P.; Dou, Jianmin; Wang, Daqi; Zhu, Peihua; Ma, Changqin; Hartnell, Regan David; Arnold, Dennis P.; Jiang, Jianzhuang
Journal Name Chemistry: A European Journal
Year Published 2005
Place of publication Germany
Publisher Wiley
Abstract 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.
Peer Reviewed Yes
Published Yes
Alternative URI http://dx.doi.org/10.1002/chem.200500214
Volume 11
Page from 7351
Page to 7357
ISSN 0947-6539
Date Accessioned 2007-11-12
Language en_AU
Faculty Other
Subject PRE2009-Organic Chemical Synthesis
URI http://hdl.handle.net/10072/21514
Publication Type Journal Articles (Refereed Article)
Publication Type Code c1x

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