Ferrocenyl-Naphthalimide Donor-Acceptor Dyads with Aromatic Spacer Groups
Ferrocenyl-Naphthalimide Donor-Acceptor Dyads with Aromatic Spacer Groups
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DOI：
10.1021/om1000452
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发表时间：
2010-06-14
期刊：
影响因子：
2.8
通讯作者：
Tagg, Tei
中科院分区：
文献类型：
--
作者：
McAdam, C. John;Robinson, Brian H.;Tagg, Tei
本文报道了一系列以二茂铁为给体、萘酰亚胺为受体的二元配合物的制备和表征。该化合物含有通过乙炔基桥连接到萘二甲酰亚胺的4-位的二茂铁-乙烯基间隔基组分，Fc CH= CH-间隔基-C C C萘二甲酰亚胺（Fc =二茂铁基），其中间隔基是1，4-苯基、4，4 ′-联苯和9，10-蒽基。二元体系的前体，卤代-间隔基-C1-C-萘酰亚胺，也被表征，其中卤代-间隔基是1-溴苯基、4-溴联苯和9-碘蒽基。各种合成策略进行检查，与连接的间隔4-乙炔基萘二甲酰亚胺，然后与乙烯基二茂铁反应证明最有效的路线。给体-间隔基-受体（D-S-A）化合物（E）-1-乙烯基二茂铁基-4-（4-乙炔基-N-甲基-1，8-萘二甲酰亚胺）苯（7）和前体化合物（E）-4-溴-4 '-（乙烯基二茂铁基）联苯（2）和4-乙炔基-4 '-（4-乙炔基-N-甲基-1，8-萘二甲酰亚胺）联苯（4），在两种萘二甲酰亚胺衍生物中的堆积主要是π-堆积相互作用。含有二茂铁基的化合物显示出预期的单电子氧化过程中的电位变化不大的间隔基团。二茂铁衍生物和它们的萘酰亚胺前体都表现出可逆的还原波。苯基和联苯化合物及其前体的单波被分配给萘酰亚胺单元的可逆单电子还原。相应的蒽衍生物显示两个可逆的还原与萘酰亚胺和蒽基部分，分别。
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-ethyny1-4'-(4-ethynyl-N-methyl-1,8-naphthalimide)biphenyl (4) are reported, with packing in the two naphthalimide derivatives dominated by offset pi-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.