Direct Observation of a Dark State in the Photocycle of a Light-Driven Molecular Motor.
Direct Observation of a Dark State in the Photocycle of a Light-Driven Molecular Motor.
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DOI：
10.1021/acs.jpca.6b09644
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发表时间：
2016-11-03
影响因子：
2.9
通讯作者：
Woutersen, Sander
中科院分区：
文献类型：
--
作者：
Amirjalayer, Saeed;Cnossen, Arjen;Browne, Wesley R.;Feringa, Ben L.;Buma, Wybren J.;Woutersen, Sander
控制光驱动分子机器的激发态性质对于实现高效率和定向功能至关重要。实现控制的一个关键挑战在于解开复杂的光动力学，特别是确定暗态所起的作用。本文利用紫外泵浦/红外探测光谱的结构灵敏度和高时间分辨率，建立了一个详细而全面的光驱动分子转子结构演化模型。这些手性拥挤烯烃衍生物的光动力学是由两个邻近的激发电子态决定的。这些“亮”和“暗”态的势能景观在整个中红外范围内产生了一个宽的激发态电子吸收带，这是第一次探测并通过量子力学计算建模。在我们的研究中观察到的瞬态红外振动指纹允许明确识别“暗”电子激发态的身份，光子的能量从该激发态转换为运动，从而为基于该结构基序调整未来分子转子的量子产率铺平道路。
Controlling the excited-state properties of light driven molecular machines is crucial to achieving high efficiency and directed functionality. A key challenge in achieving control lies in unravelling the complex photodynamics and especially in identifying the role played by dark states. Here we use the structure sensitivity and high time resolution of UV-pump/IR-probe spectroscopy to build a detailed and comprehensive model of the structural evolution of light driven molecular rotors. The photodynamics of these chiral overcrowded alkene derivatives are determined by two close-lying excited electronic states. The potential energy landscape of these “bright” and “dark” states gives rise to a broad excited-state electronic absorption band over the entire mid-IR range that is probed for the first time and modeled by quantum mechanical calculations. The transient IR vibrational fingerprints observed in our studies allow for an unambiguous identification of the identity of the “dark” electronic excited state from which the photon’s energy is converted into motion, and thereby pave the way for tuning the quantum yield of future molecular rotors based on this structural motif.
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影响因子：
2.7
作者：
García-Amorós J;Velasco D
通讯作者：
Velasco D
影响因子：
3.6
作者：
Filatov, Michael;Olivucci, Massimo
通讯作者：
Olivucci, Massimo
DOI：
10.1002/wcms.1135
发表时间：
2013-09-01
影响因子：
11.4
作者：
Filatov, Michael
通讯作者：
Filatov, Michael
DOI：
10.1002/anie.201505464
发表时间：
2015-11-09
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Galli M;Lewis JE;Goldup SM
通讯作者：
Goldup SM
影响因子：
2.3
作者：
Figgen, D;Rauhut, G;Stoll, H
通讯作者：
Stoll, H