Synthesis and Electrochemical Studies of a Series of Fluorinated Dodecaphenylporphyrins

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• 作者：Karl M. Kadish ; Eric Van Caemelbecke ; Francis D'Souza ; Min Lin ; Daniel J. Nurco ; Craig J. Medforth ; Timothy P. Forsyth ; Bé ; né ; dicte Krattinger ; Kevin M. Smith ; Shunichi Fukuzumi ; Ikuo Naka
• 刊名：Inorganic Chemistry
• 出版年：1999
• 出版时间：May 3, 1999
• 年：1999
• 卷：38
• 期：9
• 页码：2188 - 2198
• 全文大小：185K
• 年卷期：v.38,no.9(May 3, 1999)
• ISSN：1520-510X

文摘

Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (F_xDPPs) weresynthesized as model compounds for studying electronic effects in nonplanar porphyrins, and detailedelectrochemical studies of the chloroiron(III) complexes of these compounds were undertaken. The series ofporphyrins, represented as FeDPPCl and as FeF_xDPPCl where x = 4, 8 (two isomers), 12, 20, 28, or 36, couldbe reversibly oxidized by two successive one-electron transfer steps in dichloromethane to give pi.gif" BORDER=0 >-cation radicalsand pi.gif" BORDER=0 >-dications, respectively. All of the compounds investigated could also be reduced by three electrons inbenzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compoundFeDPPCl, whereas the FeF_xDPPCl complexes generally exhibited irreversible first and second reductions whichwere coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss ofthe chloride ion after generation of [Fe^IIF_xDPPCl]^-. The second chemical reaction involved a conversion betweenthe initially generated Fe(II) porphyrin pi.gif" BORDER=0 >-anion radical and the final Fe(I) porphyrin reduction product. In pyridine,three reversible one-electron reductions were observed with the second reduction affording stable Fe(II) porphyrinpi.gif" BORDER=0 >-anion radicals for all of the complexes investigated.