Formation, Chemical and Optical Properties of 1,2,5‐Triphenylpentadienyl Cation Fixed in a Rigid Dibenzobarrelene Skeleton
Formation, Chemical and Optical Properties of 1,2,5‐Triphenylpentadienyl Cation Fixed in a Rigid Dibenzobarrelene Skeleton
复制标题
固定在刚性二苯并桶烯骨架中的 1,2,5-三苯基戊二烯基阳离子的形成、化学和光学性质
DOI：
10.1002/ejoc.202200033
复制
发表时间：
2022
影响因子：
2.8
通讯作者：
Nakata Norio
中科院分区：
文献类型：
--
作者：
Ishii Akihiko;Ebina Ryota;Nakata Norio
合成了1，2，5-三苯基膦阳离子与二苯并环戊二烯骨架的稠合物。用1H和13 C核磁共振谱表征了其结构。阳离子在5-位从Et 2 O中提取氢化物，得到5-H衍生物以及乙醛和乙烯。与H2O的反应提供5-OH衍生物而不是1-OH前体。硅烷或NaBH 4的氢化物还原反应发生在3-和5-位，还原率取决于还原剂的体积。二氯甲烷中的阳离子在678、523和443 nm处表现出长波长吸收，在729 nm处表现出发射最大值，发射量子产率为0.175，其比参考的1，5-二苯基二氢呋喃阳离子更长且更大。 TD-DFT计算结果表明，这些跃迁是由1，2，5-三苯基并[1，2，5-benzobarrelene]和二苯并[1，2，5-benzobarrelene]苯环上的π-π* 激发引起的.
1,2,5‐Triphenylpentadienyl cation fused with a dibenzobarrelene skeleton was synthesized. The pentadienyl cation was persistent in the solution and characterized by1H and13C NMR spectroscopies. The cation abstracts a hydride from Et2O at the 5‐position to give the 5‐H derivative together with acetaldehyde and ethene. The reaction with H2O provided the 5‐OH derivative and not the 1‐OH precursor. The hydride reduction of the pentadienyl cation with silanes or NaBH4occurred at the 3‐ and 5‐positions, and the ratio was dependent on the bulkiness of reducing reagents. The cation in dichloromethane exhibited long‐wavelength absorptions at 678, 523, and 443 nm and an emission maximum at 729 nm with the emission quantum yield of 0.175, which are longer and larger than those of the referenced 1,5‐diphenylpentadienyl cation. TD‐DFT calculations show that the absorptions are due to the π‐π* excitations on 1,2,5‐triphenylpentadienyl and dibenzobarrelene benzene rings.