Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N-N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine

Wang Gang; Li Yazhen; Song Tingting; Shang Congdi; Yang Jiawei; Lily Makroni; Fang Yu; Liu Fengyi

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N-N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine

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Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N-N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine

机译：光致变色苯肼的荧光切换机制：N-N单键旋转辅助E / Z光异构化与亚胺不同

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Photochromic phenylhydrazones are one of the most promising candidates for a photoswitchable fluorescent probe with potential applications in various fields, but mechanistic understanding of the origin of this unique behavior is limited. In this work, we explored the emission nature and switching mechanism of a model phenylhydrazone-based fluorescent photoswitch, DMA-PHA, by means of TD-DFT and CASPT2 calculations. The fluorescence-emitting Z configuration of DMA-PHA does not involve an excited-state intramolecular proton transfer process since the resonance effect between the DMA group and the rest part of the molecule in the excited state strengthens the hydrogen bond and thus stabilizes the emissive state. The light-induced fluorescence toggling results from E <-> Z interconversion driven by an out-of-plane C=N bond torsion and assisted by a N-N single bond rotation, which in total lead to a charge separation process losing the fluorescence activity. The N-N bond rotation in phenylhydrazone further enhances the competitive nonradiative decay and reduces the photoisomerization yields. The theoretical results will provide the guidance for the rational design of novel and improved photoswitchable fluorescent probes with desired performances.

机译：光致变色苯腙是最有希望的候选人在各个领域的潜在应用光开关的荧光探针之一，但这种独特的行为起源的机械理解是有限的。在这项工作中，我们探讨了基于腙模型荧光光控开关，DMA-PHA，通过TD-DFT和CASPT2计算装置的辐射性质和交换机制。 DMA-PHA的荧光发光Z构型，因为DMA组和在激发态的分子的其余部分的部分之间的共振效应增强了氢键，从而稳定了发射状态不涉及激发态分子内质子转移过程。所述光诱导荧光法给E切换结果< - >ž互利用out-of-平面中的C = N键的扭转驱动并辅助由N-N单键的旋转中，在总铅到电荷分离过程中丢失的荧光活性。在苯腙的N-N键的旋转进一步提高竞争非辐射衰变并降低了光异构化的产率。理论结果将提供新颖的合理设计的指导和改进的具有所需性能的光开关的荧光探针。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2020年第32期|共9页
作者
Wang Gang; Li Yazhen; Song Tingting; Shang Congdi; Yang Jiawei; Lily Makroni; Fang Yu; Liu Fengyi;
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Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

Shaanxi Normal Univ Key Lab Macromol Sci Shaanxi Prov Sch Chem &

Chem Engn Key Lab Appl Surface &

Colloid Chem Minist Educ Xian 710119 Shaanxi Peoples R China;

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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
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1. Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N-N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine [J] . Wang Gang, Li Yazhen, Song Tingting, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2020,第32期

机译：光致变色苯肼的荧光切换机制：N-N单键旋转辅助E / Z光异构化与亚胺不同
2. Synthesis and photochromic properties of some N-phthalimide azo-azomethine dyes. A DFT quantum mechanical calculations on imine-enamine tautomerism and trans-cis photoisomerization [J] . Georgiev Anton, Stoilova Ani, Dimov Deyan, Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy . 2019,第期

机译：一些n-邻苯二甲酰亚胺胺染料的合成和光致变色特性。亚胺 - 烯胺互变异构型和跨型光硅蛋白化的DFT量子力学计算
3. Photochemical anti-syn isomerization around the -N-N= bond in heterocyclic imines [J] . Hricovini Michal, Asher James, Hricovini Milos RSC Advances . 2020,第10期

机译：在-N-N =杂环膜中的光化学抗SYN异构化
4. Evidence of N-N single bond as a hindrance of electron delocalization in cyclic and acyclic azines [C] . Jiri Ludvik, Jiri Urban, Jaromir Jirkovsky, International Symposium on Reactive Intermediates in Organic and Biological Electrochemistry . 2001

机译：N-N单键的证据是循环和共晶的电子临床化的障碍
5. Mechanisms in Single Molecule Fluorescence Imaging: From Photophysics to Biological Applications [D] . Gidi, Yasser. 2020

机译：单分子荧光成像的机制：从光学药物到生物应用
6. The Mechanism of N-N Double Bond Cleavage by an Iron(II)-Hydride Complex [O] . Sarina M. Bellows, Nicholas A. Arnet, Prabhuodeyara M. Gurubasavaraj, -1

机译：铁（II）-氢化物配合物裂解N-N双键的机理
7. Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: NN Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine [O] . -1

机译：光致变色苯肼的荧光切换机制：NN单键旋转辅助E / Z光异构化与亚胺不同

Fluorescence Toggling Mechanism of Photochromic Phenylhydrazones: N-N Single Bond Rotation-Assisting E/Z Photoisomerization Differs from Imine

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