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基于硫代靛红的三氧杂环壬二烯:电子和几何性质的 3D 多态转变。

Hemithioindigo-Based Trioxobicyclononadiene: 3D Multiswitching of Electronic and Geometric Properties.

机构信息

Department of Chemistry and Pharmacy, Friedrich-Alexander Universität Erlangen-Nürnberg, Nikolaus-Fiebiger-Str. 10, 91058 Erlangen, Germany.

Department of Chemistry and Center for Integrated Protein Science (CIPSM), Ludwig-Maximilians Universität München, Butenandtstr. 5-13, 81377 Munich, Germany.

出版信息

J Am Chem Soc. 2022 Feb 23;144(7):2847-2852. doi: 10.1021/jacs.1c12364. Epub 2022 Feb 14.

DOI:10.1021/jacs.1c12364
PMID:35157795
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8874893/
Abstract

Molecular photoswitches that offer simultaneous precise control over geometrical and electronic changes are rare yet highly sought tools for the development of responsive nanosystems. Here we present such an advantageous combination of property control within a novel multiphotoswitch architecture. Hemithioindigo-based trioxobicyclononadiene (HTI-TOND) offers a rigid three-dimensional molecular structure that undergoes different exotic rearrangement reactions upon photochemical and thermal signaling. Three to four different states with distinct geometric and electronic properties can be accessed reversibly in high yields within this molecular framework. Thus, a highly promising and unique switching tool has become available to instill the next level of addressability at the smallest scales.

摘要

同时提供对几何形状和电子变化进行精确控制的分子光开关非常罕见,但对于开发响应性纳米系统而言,它们是高度需要的工具。在这里,我们在一种新颖的多光开关结构中展示了这种有利的特性控制组合。基于半硫靛的三氧杂双环壬二烯(HTI-TOND)提供了刚性的三维分子结构,在光化学和热信号作用下会发生不同的奇特重排反应。在这个分子框架内,可以以高收率可逆地进入三种到四种具有不同几何形状和电子特性的不同状态。因此,一种非常有前途和独特的开关工具已经可用,为最小尺度上的下一层次的寻址能力提供了可能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/c622bc09e480/ja1c12364_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/e70b153be54f/ja1c12364_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/43372ddc4f52/ja1c12364_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/40966982f5b5/ja1c12364_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/c622bc09e480/ja1c12364_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/e70b153be54f/ja1c12364_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/43372ddc4f52/ja1c12364_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/40966982f5b5/ja1c12364_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1c11/8874893/c622bc09e480/ja1c12364_0003.jpg

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本文引用的文献

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Photoswitchable catalysis based on the isomerisation of double bonds.基于双键异构化的光开关催化
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Taming the Complexity of Donor-Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway.
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A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches.一种用于高性能二芳基半硫代靛蓝光开关的交叉共轭方法。
Chem Sci. 2023 May 1;14(21):5734-5742. doi: 10.1039/d2sc06939c. eCollection 2023 May 31.
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Heterocyclic Hemithioindigos: Highly Advantageous Properties as Molecular Photoswitches.杂环半硫靛:作为分子光开关具有高度有利的性质。
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202210855. doi: 10.1002/anie.202210855. Epub 2022 Sep 21.
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Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems.分子光开关在智能材料和生物系统中的最新应用。
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New molecular switch architectures.新型分子开关结构。
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