Europium Triple-Decker Complexes Containing Phthalocyanine and Nitrophenyl鈥揅orrole Macrocycles

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• 作者：Guifen Lu ; Jing Li ; Xiaoqin Jiang ; Zhongping Ou ; Karl M. Kadish
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：September 21, 2015
• 年：2015
• 卷：54
• 期：18
• 页码：9211-9222
• 全文大小：660K
• ISSN：1520-510X

文摘

A series of europium triple-decker complexes containing phthalocyanine and nitrophenyl鈥揷orrole 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鈥?i>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鈥? 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]^{鈭?/sup> in a separate one-electron transfer step at potentials between 鈭?.12 and 鈭?.42 V versus saturated calomel electrode.}