9,10-Dicyanoanthracene-Photosensitized Elimination of 1,1′-Binaphthalene from Dinaphthyl Methylphosphonate and Trinaphthyl Phosphate through the Termolecular Interaction in the Singlet Excited State
作者:Mitsunobu Nakamura、Masamichi Miki、Tetsuro Majima
DOI:10.1246/bcsj.72.2103
日期:1999.9
9,10-Dicyanoanthracene (DCA) photosensitized intramolecular binaphthalene elimination of dinaphthyl methylphosphonates and trinaphthyl phosphates occurred through an exciplex between the singlet excited DCA (1DCA*) and the naphthyl group of dinaphthyl methylphosphonate and trinaphthyl phosphates in tetrahydrofuran, 1,4-dioxane, and benzene. Diethyl mononaphthyl phosphates also formed an exciplex with 1DCA*, while no reaction occurred. The binaphthalene elimination occurs via the intramolecular quenching of the exciplex by the second naphthyl group of dinaphthyl methylphosphonate or trinaphthyl phosphate, while the exciplex between the mononaphthyl phosphate and 1DCA* decays to give the starting compounds. The lifetime of the exciplex between the trinaphthyl phosphate and 1DCA* was shorter than that between the mononaphthyl phosphate and 1DCA*. The termolecular interaction (teraromatic groups interaction) of 1DCA* and two naphthyl groups of dinaphthyl methylphosphonate or trinaphthyl phosphate is suggested by the emission observation of the termolecular interaction of two naphthyl groups of trinaphthyl phosphate and 1,4-dicyanobenzene in the singlet excited state during the quenching of the intramolecular excimer of dinaphthyl methylphosphonate or trinaphthyl phosphates by 1,4-dicyanobenzene. The O–P(O)–O spacer is necessary for the binaphthalene elimination during the termolecular interaction in the singlet excited state.
9,10-二氰基蒽 (DCA) 光敏分子内联萘消除甲基膦酸二萘酯和磷酸三萘酯是通过单线态激发 DCA (1DCA*) 与四氢呋喃、1,4-二恶烷中的甲基膦酸二萘酯和磷酸三萘酯的萘基之间的激基复合物发生的,和苯。二乙基单萘基磷酸酯也与 1DCA* 形成激基复合物,但没有发生反应。联萘消除是通过甲基膦酸二萘酯或磷酸三萘酯的第二个萘基对激基复合物的分子内猝灭而发生的,而磷酸一萘酯和 1DCA* 之间的激基复合物衰变得到起始化合物。磷酸三萘酯和1DCA*之间的激基复合物的寿命比磷酸单萘酯和1DCA*之间的激基复合物的寿命短。 1DCA* 与甲基膦酸二萘酯或磷酸三萘酯的两个萘基之间的术语分子相互作用(芳香族基团相互作用)是通过在单重激发态下对磷酸三萘酯和 1,4-二氰基苯的两个萘基的分子间相互作用的发射观察得出的。甲基膦酸二萘酯或磷酸三萘酯的分子内准分子被1,4-二氰基苯猝灭。 O-P(O)-O 间隔基对于单线态激发态分子相互作用期间联萘消除是必要的。