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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 ChiFung,
Ng Dennis K. P.,
Dou Jianmin,
Wang Daqi,
Zhu Peihua,
Ma Changqin,
Hartnell Regan D.,
Arnold Dennis P.,
Jiang Jianzhuang
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500214
Subject(s) - homoleptic , isoindole , chemistry , phthalocyanine , crystallography , square antiprism , ligand (biochemistry) , crystal structure , metal , valence (chemistry) , stereochemistry , ion , lanthanide , biochemistry , receptor , organic chemistry
Homoleptic bis(phthalocyaninato) rare‐earth double‐deckers complexes [M III {Pc(α‐OC 5 H 11 ) 4 } 2 ] (M=Eu, Y, Lu; Pc(α‐OC 5 H 11 ) 4 =1,8,15,22‐tetrakis(3‐pentyloxy)phthalocyaninate) have been prepared by treating the metal‐free phthalocyanine H 2 Pc(α‐OC 5 H 11 ) 4 with the corresponding M(acac) 3 ⋅ n H 2 O (acac=acetylacetonate) in refluxing n ‐octanol. Due to the C 4 h symmetry of the Pc(α‐OC 5 H 11 ) 4 ligand and the double‐decker structure, all the reactions give a mixture of two stereoisomers with C 4 h 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 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 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 π–π interaction between the two Pc(α‐OC 5 H 11 ) 4 rings is weaker than that for the corresponding unsubstituted or β‐substituted bis(phthalocyaninato) analogues.