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Chemistry

氢化光开关光异构化量子产率的测定

Published: February 7th, 2022

DOI:

10.3791/63398

1Department of Chemistry, Chung-Ang University
* These authors contributed equally

光异构化量子产率是研究新开发的光开关时应准确确定的基本光物理性质。在这里,我们描述了一组测量光致变色腙的光异构化量子产率的程序,作为模型双稳态光开关。

经历光驱动结构转变的光开关有机分子是构建适应性分子系统的关键成分,它们被用于各种应用。在大多数使用光开关的研究中,仔细测定了几种重要的光物理性质,例如吸收和发射的最长,摩尔衰减系数,荧光寿命和光异构化量子产率,以研究其电子态和过渡过程。然而,在典型的实验室环境中,光异构化量子产率的测量,光异构化相对于吸收光子的效率通常很复杂且容易出错,因为它需要基于适当的积分方法实施严格的光谱测量和计算。本文介绍了一组使用光致变色腙测量双稳态光开关的光异构化量子产率的程序。我们预计本文将成为研究日益开发的双稳态光开关的有用指南。

光致变色有机分子在广泛的科学学科中引起了相当大的关注,因为光是一种独特的刺激,可以无创地使系统远离其热力学平衡1。以适当能量照射光允许以高时空精度234对光开关进行结构调制。由于这些优点,已经开发出基于双键(例如,二苯乙烯,偶氮苯,亚胺,富马酰胺,硫代金戈)和环开/闭合(例如,螺旋藻,二噻吩,黄酮,供体 - 受体Stenhouse加合物)的构型异构化的各种类型的光开关,并被用作各种长度尺度的自适应材料的核心成分。光开关的代表性应用涉及光致变色材料、药物递送、可切换受体和通道、信息或能量存储以及分子机器56789101112。在大多数介绍新设计的光开关的研....

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1. 1光静止状态下的H NMR光谱采集(PSS)

  1. 在含有4.2mg(0.01 mmol)hydrazone开关1的天然石英NMR管中,加入1.0 mL氘化二甲基亚砜(DMSO-d 6)。将一半的溶液转移到另一个NMR管中。
  2. 将其中一个 NMR 管放置在配备 436 nm 带通滤光片的氙弧灯前 1 cm 处。开始照射核磁共振样品,每天记录 1H 核磁共振光谱,直到当开关 1 达到 PSS 时.......

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在具有436nm光的NMR管中照射1(初始状态下Z:E = 54:46)时,由于腙C = N键的显性Z到E异构化,1-E的比例增加(图1)。异构体比可以很容易地从1H NMR光谱中不同异构体的相对信号强度中获得(图2)。在436nm处照射5天后,样品达到含有92%1-E的PSS。由于样品浓度高(10 mM)和光源.......

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已经开发了各种策略来调整光开关的光谱和开关特性,并且光开关的寄存器正在迅速扩展28。因此,正确确定它们的光物理性质至关重要,我们预计本文中总结的方法将成为实验者的有用指南。前提是室温下的热弛豫速率非常慢,测量PSS组成在不同照射波长下、纯异构体的摩尔衰减系数、有效摩尔光子通量、沙伪量子产率可以估计单向光异构化量子产率。本研究提出的实验结果?.......

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这项工作得到了2019年中央大学研究补助金和韩国国家研究基金会(NRF-2020R1C1C1011134)的支持。

....

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NameCompanyCatalog NumberComments
1,10-phenanthrolineSigma-Aldrich131377-2.5G
340 nm bandpass filter, 25 mm diameter, 10 nm FWHMEdmund Optics#65-129
436 nm bandpass filter, 25 mm diameter, 10 nm FWHMEdmund Optics#65-138
Anhydrous sodium acetateAlfa aesarA13184.30
Dimethyl sulfoxideSamchunD1138HPLC grade
Dimethyl sulfoxide-d6Sigma-Aldrich151874-25g
Gemini 2000; 300 MHz NMR spectrometerVarian
H2SO4Duksan235
Heating bathJeioTechCW-05G
MestReNova 14.1.1Mestrelab Research S.L., https://mestrelab.com/
Natural quartz NMR tubeNorellS-5-200-QTZ-7
Potassium ferrioxalate trihydrateAlfa aesar31124.06
Quartz absorption cellHellmaHE.110.QS10
UV-VIS spectrophotometerScincoS-3100
Xenon arc lampThorlabsSLS205Fiber adapter was removed

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