Europium Triple-Decker Complexes Containing Phthalocyanine and Nitrophenyl–Corrole Macrocycles

A series of europium triple-decker complexes containing phthalocyanine and nitrophenyl–corrole macrocycles were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. The examined compounds are represented as Eu2[Pc­(OC4H9)8]2­[Cor­(Ph) n (NO2Ph)3–n ], where...

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Bibliographic Details
Published in:Inorganic chemistry 2015-09, Vol.54 (18), p.9211-9222
Main Authors: Lu, Guifen, Li, Jing, Jiang, Xiaoqin, Ou, Zhongping, Kadish, Karl M
Format: Article
Language:English
Subjects:
Calomel electrode
Europium
Macrocyclic compounds
Oxidation
Parents
Phenyls
Pyridines
Reduction
Spectroscopy
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Summary:A series of europium triple-decker complexes containing phthalocyanine and nitrophenyl–corrole macrocycles were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. The examined compounds are represented as Eu2[Pc­(OC4H9)8]2­[Cor­(Ph) n (NO2Ph)3–n ], where n varies from 0 to 3, Pc­(OC4H9)8 represents the phthalocyanine macrocycle, and Cor indicates the corrole macrocycle having phenyl (Ph) or nitrophenyl (NO2Ph) meso substituents. Three different methods were used for syntheses of the target complexes, two of which are reported here for the first time. Each examined compound undergoes five reversible one-electron oxidations and 3–5 one-electron reductions depending upon the number of NO2Ph substituents. The nitrophenyl groups on the meso positions of the corrole are highly electron-withdrawing, and this leads to a substantial positive shift in potential for the five oxidations and first reduction in CH2Cl2, PhCN, or pyridine as compared to the parent triple-decker compound with a triphenylcorrole macrocycle. The measured E 1/2 values are linearly related to the number of NO2Ph groups on the corrole, and the relative magnitude of the shift in potential for each redox reaction was used in conjunction with the results from thin-layer spectro-electrochemistry to assign the initial site of oxidation or reduction on the molecule. The nitrophenyl substituents are also redox-active, and each is reduced to [C6H4NO2]− in a separate one-electron transfer step at potentials between −1.12 and −1.42 V versus saturated calomel electrode.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.5b01713