Dynamic effects of the bridged structure on the quantum yield of the <i>cis</i> → <i>trans</i> photoisomerization of azobenzene
Dynamic effects of the bridged structure on the quantum yield of the <i>cis</i> → <i>trans</i> photoisomerization of azobenzene
复制标题
桥联结构对偶氮苯<i>cis</i>→<i>trans</i>光异构化量子产率的动态影响
DOI：
10.1039/d2cp02418g
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发表时间：
2022
影响因子：
3.3
通讯作者：
Matsubara Toshiaki
中科院分区：
文献类型：
--
作者：
Nagamori Keigo;Haze Misato;Nakata Hiroyuki;Zingsheim Oliver;Yamasaki Katsuyoshi;Kohguchi Hiroshi;Matsubara Toshiaki
采用非绝热分子动力学模拟方法对二苯胺重氮嘧啶顺式→反式光异构化进行了研究，以确定其桥接结构如何导致该异构化的最高量子产率。与偶氮苯类似，当二苯胺重氮嘧啶被激发到S1态时，通过- nn -部分通过S1/S0锥形交点的踏板运动，它会异构化为转化态。然而，由于分子内振动能量的重新分配较快，二苯胺重氮嘧啶的激发态寿命较短。桥接结构降低了自由度，除了那些驱动异构化的自由度。因此，动能被选择性地分配到- nn -段踏板运动的特定法向模式上，并被有效地用于异构化转化，这被认为是异构化收率提高的主要原因。
A nonadiabatic molecular dynamics simulation was performed for the cis → trans photoisomerization of diindane diazocine to determine how its bridged structure results in the highest reported quantum yield for this isomerization. Similar to azobenzene, when diindane diazocine is excited to the S1 state, it isomerizes to the trans form by a pedal motion of the –NN– moiety passing through the S1/S0 conical intersection. However, due to the faster intramolecular vibrational energy redistribution, the excited state lifetime of diindane diazocine is shorter. The bridged structure reduces the degrees of freedom, other than those that drive the isomerization. Therefore, the kinetic energy is selectively distributed to the specific normal mode for the pedal motion of the –NN– moiety, and it is efficiently utilized for the isomerization to the trans form, which is considered a major reason for the increased isomerization yield.