Benzo[e]pyrene Skeleton Dipyrylium Dication with a Strong Donor-Acceptor-Donor Interaction, and Its Two-Electron Reduced Molecule
Benzo[e]pyrene Skeleton Dipyrylium Dication with a Strong Donor-Acceptor-Donor Interaction, and Its Two-Electron Reduced Molecule
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DOI：
10.1002/chem.201101708
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发表时间：
2011-12-01
影响因子：
4.3
通讯作者：
Nishihara, Hiroshi
中科院分区：
文献类型：
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作者：
Rao, Koya Prabhakara;Kondo, Mio;Nishihara, Hiroshi
供体-受体-供体（D-A-D）共轭分子1，4-双二芳氨基苯乙炔基蒽醌（1，4-Am（2）Aq）和1，4-bis二茂铁基乙炔基蒽醌（1，4-Fc（2）Aq），与双（三氟甲砜）酰亚胺酸（TFSIH），得到1，4-双（二芳基氨基苯基或二茂铁基）二吡喃鎓盐[1，4-R（2）Pyl（2）]（TFSI）（2）（R = Am或Fc），其具有类似于芳族苯并[e]芘型骨架的新型平面五环结构。[1，4-Am（2）Pyl（2）]（TFSI）（2）可被还原为中性分子[1，4-Am（2）Pyl（2）]（0），该分子稳定且保持苯并[e]芘型骨架。据我们所知，这是第一个含氧原子的多环芳烃与22（4 n +2）π电子。所得稠环苯并[e]芘型骨架化合物显示出与具有二萘嵌苯型骨架的[1，5-Am（2）Pyl（2）]（TFSI）（2）显著不同的物理和化学性质。
The donor-acceptor-donor (D-A-D) conjugated molecules 1,4-bis(diarylaminophenylethynyl)anthraquinone (1,4-Am(2)Aq) and 1,4-bis(ferrocenylethynyl)anthraquinone (1,4-Fc(2)Aq), undergo a double proton cyclization reaction with bis(trifluoromethanesulfone) imide acid (TFSIH) to yield 1,4-bis(diarylaminophenyl or ferrocenyl) dipyrylium salts [1,4-R(2)Pyl(2)](TFSI)(2) (R = Am or Fc) with novel planar pentacyclic structures similar to the aromatic benzo[e]pyrene-type skeleton. [1,4-Am(2)Pyl(2)](TFSI)(2) could be reduced to give the neutral molecule [1,4-Am(2)Pyl(2)](0), which is stable and maintains the benzo[e]pyrene-type skeleton. To the best of our knowledge, this is the first oxygen-atom-containing polycyclic aromatic hydrocarbon with 22 (4n+2) pi-electrons. The obtained condensed-ring benzo[e]pyrene-type skeleton compounds show physical and chemical properties that are significantly different from those of [1,5-Am(2)Pyl(2)](TFSI)(2), which has a perylene-type skeleton.