芳香偶氮吡唑光异构化的非绝热动力学模拟
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- 英文论文题名：Z-E Photoisomerization Mechanism of Arylazopyrazoles:Nonadiabatic Dynamics Simulations
- 论文作者：王雅婷 ; 刘向洋 ; 刘丽虹 ; 崔刚龙 ; 方维海
- 英文论文作者：Yating Wang ; Xiang-Yang Liu ; Lihong Liu ; Ganglong Cui ; Wei-Hai Fang ; Key Laboratory of Theoretical and Computational Photochemistry ; Ministry of Education ; College of Chemistry ; Beijing Normal University
- 年：2016
- 作者机构：北京师范大学化学学院理论与计算光化学教育部重点实验室;
- 论文关键词：非绝热动力学 ; 光异构化 ; 锥形交叉点 ; 光开关
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十九分会：化学中的量子与经典动力学
- 语种：中文
- 分类号：O626.21
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十九分会 ; 化学中的量子与经典动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：110k
- 原文格式：D
- 会议级别：全国
摘要
实验研究发现五元芳香偶氮吡唑具有极好的光异构化效率及热稳定性。然而,其光物理和光化学机理尚不清楚。我们对两种芳香偶氮吡唑(Z11和Z8)进行了电子结构计算和非绝热动力学模拟,得到两个手性锥形交叉点,发现两个超快的手性S_1激发态弛豫路径。对于Z11,两个手性S_1激发态弛豫路径具有构象专一性;然而,对于Z8,两个路径对激发态衰减的贡献相当。进一步的分析表明,苯基与吡唑基团间的空间相互作用在控制S_1激发态衰减动力学的路径选择上发挥了关键作用。这种新颖的激发态路径选择性是首次被提出。最后,我们对芳香偶氮吡唑和偶氮苯的光异构化机理和激发态衰减动力学的异同点进行了比较。
A novel class of five-membered arylazopyrazole photoswitches are recently found to exhibit excellent quantitative photoswitching and high thermal stability. However, the photoisomerization mechanism is unclear. We have first employed electronic structure calculations and nonadiabatic dynamics simulations to explore the Z-E photoisomerization mechanism and excited-state decay dynamics of two arylazopyrazole photoswitches(Z11 and Z8). We have optimized two chiral S_1/S_0 conical intersections and found that the associated two chiral S_1 relaxation paths are barrierless and efficient. For Z11, these two chiral S_1 relaxation paths are conformer-specific; whereas, for Z8, both paths contribute evenly to the S_1 excited-state decay. Further analysis shows that steric interaction between pyrazole and phenyl groups play a key element in regulating the path selectivity of the S_1 decay dynamics. This novel excited-state path selectivity is first reported. Finally, the similarities and dissimilarities of photoisomerization mechanism and decay dynamics between arylazopyrazoles and azobenzenes are also presented.
A novel class of five-membered arylazopyrazole photoswitches are recently found to exhibit excellent quantitative photoswitching and high thermal stability. However, the photoisomerization mechanism is unclear. We have first employed electronic structure calculations and nonadiabatic dynamics simulations to explore the Z-E photoisomerization mechanism and excited-state decay dynamics of two arylazopyrazole photoswitches(Z11 and Z8). We have optimized two chiral S_1/S_0 conical intersections and found that the associated two chiral S_1 relaxation paths are barrierless and efficient. For Z11, these two chiral S_1 relaxation paths are conformer-specific; whereas, for Z8, both paths contribute evenly to the S_1 excited-state decay. Further analysis shows that steric interaction between pyrazole and phenyl groups play a key element in regulating the path selectivity of the S_1 decay dynamics. This novel excited-state path selectivity is first reported. Finally, the similarities and dissimilarities of photoisomerization mechanism and decay dynamics between arylazopyrazoles and azobenzenes are also presented.
引文
[1]Siewertsen,R.;Neumann,H.;Buchheim-Stehn,B.;Herges,R.;Renth,F.;Temps,F.J.Am.Chem.Soc.2009,131:155914.
[2]Cui,G.L.;Lan,Z.G.;Thiel,W.J.Am.Chem.Soc.2012,134:1662.
[3]Weingart,O.;Lan,Z.G.;Koslowski,A.;Thiel,W.J.Phys.Chem.Lett.2011,2:1506.
[4]Cui,G.L.;Thiel,W.Phys.Chem.Chem.Phys.2012,14:12378.
[5]Xie,B.B.;Xia,S.H.;Chang,X.P.;Cui,G.L.Phys.Chem.Chem.Phys.2016,18:403.
[2]Cui,G.L.;Lan,Z.G.;Thiel,W.J.Am.Chem.Soc.2012,134:1662.
[3]Weingart,O.;Lan,Z.G.;Koslowski,A.;Thiel,W.J.Phys.Chem.Lett.2011,2:1506.
[4]Cui,G.L.;Thiel,W.Phys.Chem.Chem.Phys.2012,14:12378.
[5]Xie,B.B.;Xia,S.H.;Chang,X.P.;Cui,G.L.Phys.Chem.Chem.Phys.2016,18:403.
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