Solvent Effects on the Photoamination of 1-Amino-2,4-dibromoanthraquinone. II. Dual Mode of the Photoamination in Ethanol via the S1(1CT) and T1(3CT) States
Solvent Effects on the Photoamination of 1-Amino-2,4-dibromoanthraquinone. II. Dual Mode of the Photoamination in Ethanol via the S1(1CT) and T1(3CT) States
复制标题
溶剂对 1-氨基-2,4-二溴蒽醌光胺化的影响。
DOI：
10.1246/bcsj.53.154
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发表时间：
1980
影响因子：
4
通讯作者：
M. Hida
中科院分区：
文献类型：
--
作者：
H. Inoue;Tsutomu Shinoda;M. Hida
研究了1-氨基-2，4-二溴蒽醌（1）与正丁胺在乙醇中的光胺化反应。在空气气氛（Φair=1.7×10−3，ΦN2=2.3×104，其中[丁胺]=5.00×10−2 mol/dm 3）下加速反应。详细的动力学研究表明，在氮气下，光胺化通过T1（3CT）状态进行填充的系统间穿越从S1（1CT）状态，而在空气中，它进行通过T1（3CT）和S1（1CT）状态。后一种途径在空气中包括S1（1CT）态和氧之间的相互作用，以形成激基复合物或碰撞复合物，如[AQδ+···O2δ−]。1在乙醇中的失活常数比在苯中的失活常数小一个数量级，比1-氨基蒽醌在苯中的失活常数大一个数量级。结合激发态能量图和溴在1.
The photoamination of 1-amino-2,4-dibromoanthraquinone (1) by butylamine in ethanol was investigated. The reaction was accelerated under an air atmosphere (Φair=1.7×10−3, ΦN2=2.3×104, where [butylamine]=5.00×10−2 mol/dm3). A detailed kinetic study indicated that, under nitrogen, the photoamination proceeded via the T1(3CT) state populated by the intersystem crossing from the S1(1CT) state, while under air it proceeded via both the T1(3CT) and the S1(1CT) states. The latter pathway under air included an interaction between the S1(1CT) state and oxygen to form an exciplex or a collisional complex such as [AQδ+···O2δ−]. The deactivation constant from the T1(3CT) of 1 in ethanol was revealed to be one order of magnitude smaller than that in benzene and one order magnitude larger than that of 1-aminoanthraquinone in benzene. These results were discuessd in relation to the energy diagram in the excited state and the intramolecular heavy-atom effect of bromine in 1.