In-situ NMR spectroscopic investigations of the organic photochromism in spiropyran and spiroxazine norbornens and their homopolymers

螺吡喃和螺恶嗪降冰片烯及其均聚物有机光致变色的原位核磁共振波谱研究

基本信息

批准号：
323314751
负责人：
Professorin Dr. Christina Marie Thiele
金额：
--
依托单位：
Arbeitskreis Thiele
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2016
资助国家：
德国
起止时间：
2015-12-31 至 2020-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/323314751?language=en
关键词：
situ NMR spectroscopic investigations organic

项目摘要

Upon irradiation with ultraviolet light (UV) spiropyranes and -oxazines show a change in color mostly from colorless to purple. This change in color is caused by a reversible ring opening reaction from the closed spiro- to the open merocyanine-form. The changes induced in physical properties, like the dipole moment, are used for the design of stimuli responsive materials. For the development of such materials, parameters like the degree of conversion to the open form upon irradiation or reaction rates of the thermal ring closing reaction are important. Furthermore these properties are related to the conditions present (solvent, temperature, etc.). The open merocyanine is stabilized by polar solvents, e.g., and thus thermal back reaction is slowed down. A goal of the proposed project is the investigation of the organic photochromism of monomeric and polymeric spiropyran and -oxazine-norbornenes with in-situ NMR spectroscopy. The use and development of NMR-spectroscopic methods to investigate organic photochromism is a main objective of the proposed project. Spiropyrans show degradation reactions upon irradiation. A deeper and systematic understanding of the pathways of photodegradation of spiropyran and spiroxazine norbornens is also in the focus of our investigations, as these limit the applicability of such systems. Furthermore the interaction of spiropyrans and -oxazine with (metal) ions is within the scope of this project as such interactions can have an influence on the photochromic behavior of spiropyrans and -oxazines. A deeper knowledge of the scope of these interactions would allow for a targeted use of ions to influence transport properties in mesoporous films. The monomers and polymers are synthesized in the the group of Andrieu-Brunsen and shall be used for the development of photocontrollable ionic transport in mesoporus silica-films. Results obtained from our in-situ NMR investigations of such spiropyrans and -oxazines with respect to photodecomposition reactions can then be used to improve before mentioned hybrid materials.

用紫外线（UV）螺旋酸辐照（紫外线）和 - 氧嗪的颜色变化大部分从无色变为紫色。这种颜色的变化是由从封闭的螺旋 - 到开放蛋白烯氨酸形式的可逆环开反应引起的。物理性质中引起的变化（如偶极力矩）用于设计刺激响应材料。为了开发此类材料，诸如辐照或热环关闭反应的反应速率的转化程度之类的参数很重要。此外，这些特性与存在的条件（溶剂，温度等）有关。开放式蛋白氨酸通过极性溶剂稳定，例如，因此热反应放慢了速度。拟议项目的一个目标是研究单体和聚合物螺旋桨和氧嗪 - 诺尔烯烯的有机光致变色，并具有原位NMR光谱法。 NMR-SpectRoscotic方法研究有机光更色素主义的使用和开发是拟议项目的主要目标。螺旋桨在照射时显示出降解反应。我们对螺旋形和螺丝嗪悬嗪光降解的途径的更深入而系统的理解也是我们研究的重点，因为这些限制了此类系统的适用性。此外，螺旋罗蛋白酶和 - 恶嗪与（金属）离子的相互作用在该项目的范围内，因为这种相互作用可能会影响螺内螺旋体和 - 恶心的光致变色行为。对这些相互作用范围的更深入了解将允许有针对性地使用离子来影响介孔膜中的运输特性。单体和聚合物在Andrieu-Brunsen组中合成，应用于在中层硅胶中开发可控制的离子转运。从我们对这些螺旋吡烷和 - 氧嗪相对于光二次组成反应的原位NMR研究获得的结果可以用于改进，然后再提及上述杂交材料。

项目成果

期刊论文数量（6）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Photoswitchable Intramolecular Hydrogen Bonds in 5-Phenylazopyrimidines Revealed By In Situ Irradiation NMR Spectroscopy.

原位辐照核磁共振波谱揭示 5-苯基氮杂嘧啶中的光可切换分子内氢键

DOI：
10.1002/chem.201705146
发表时间：
2018
期刊：
Chemistry
影响因子：
0
作者：
E. Procházková;L. Čechová;J. Kind;Z. Janeba;C. M. Thiele;M. Dračínský
通讯作者：
M. Dračínský

In situ Switching of Site-Selectivity with Light in the Acetylation of Sugars with Azo-Peptide Catalysts.

DOI：
10.1021/acs.joc.9b01913
发表时间：
2019-11
期刊：
The Journal of organic chemistry
影响因子：
0
作者：
Dominik Niedek;Frederik R. Erb;C. Topp;Alexander Seitz;R. Wende;A. Eckhardt;J. Kind;D. Herold;C. Thiele;P. Schreiner
通讯作者：
Dominik Niedek;Frederik R. Erb;C. Topp;Alexander Seitz;R. Wende;A. Eckhardt;J. Kind;D. Herold;C. Thiele;P. Schreiner

Photochromic dithienylethenes characterized by in situ irradiation NMR-spectroscopy and electrochemically induced responsiveness on gold substrates

通过原位辐照核磁共振波谱和金基底上的电化学诱导响应表征光致变色二噻吩乙烯