Ferrocenyl−Naphthalimide Donor−Acceptor Dyads with Aromatic Spacer Groups

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• 作者：C. John McAdam ; Brian H. Robinson ; Jim Simpson ; Tei Tagg
• 刊名：Organometallics
• 出版年：2010
• 出版时间：June 14, 2010
• 年：2010
• 卷：29
• 期：11
• 页码：2474-2483
• 全文大小：965K
• 年卷期：v.29,no.11(June 14, 2010)
• ISSN：1520-6041

文摘

The preparation and characterization of a series of dyads containing ferrocene donor and naphthalimide acceptor units, separated by aromatic spacer groups, are reported. The compounds contain a ferrocene-ethenyl spacer component linked to the 4-position of a naphthalimide by an ethynyl bridge, Fc−CH═CH−spacer−C≡C−naphthalimide (Fc = ferrocenyl), where the spacers are 1,4-phenyl, 4,4′-biphenyl, and 9,10-anthryl. Precursors to the dyad systems, halo-spacer−C≡C−naphthalimide, are also characterized where the halo-spacers are 1-bromophenyl, 4-bromobiphenyl, and 9-iodoanthryl. Various synthetic strategies are examined, with attachment of the spacer to 4-ethynylnaphthalimide followed by reaction with ethenylferrocene proving the most effective route. Crystal structures of the donor−spacer−acceptor (D−S−A) compound (E)-1-ethenylferrocenyl-4-(4-ethynyl-N-methyl-1,8-naphthalimide)benzene (7) and the precursor compounds (E)-4-bromo-4′-(ethenylferrocenyl)biphenyl (2) and 4-ethynyl-4′-(4-ethynyl-N-methyl-1,8-naphthalimide)biphenyl (4) are reported, with packing in the two naphthalimide derivatives dominated by offset π-stacking interactions. Compounds containing the ferrocenyl groups show the anticipated one-electron oxidation processes at potentials that vary little with the spacer groups. Both the ferrocenyl derivatives and their naphthalimide precursors show reversible reduction waves. The single wave for the phenyl and biphenyl compounds and their precursors is assigned to reversible one-electron reduction of the naphthalimide unit. The corresponding anthracene derivatives display two reversible reductions associated with the naphthalimide and the anthryl moieties, respectively.