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

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

DOI:
10.1039/c9tc04495g
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发表时间:
2019
影响因子:
6.4
通讯作者:
M. Gallei
M. Gallei
中科院分区:
材料科学2区
文献类型:
--
作者:
J. von Irmer;F. Frieß;D. Herold;J. Kind;C. M. Thiele;M. Gallei

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包含小分子和聚合物的光致变色化合物已经显示在用于作为传感器和(纳米)器件的应用的刺激响应材料领域中具有极大的兴趣。在这方面,二噻吩基乙烯(DTE)已被证明是特别有价值的,因为它们对化学品的耐受性和它们的良好稳定性使它们在具有不同光学性质的开放和闭合结构之间可调谐和可逆地切换。通过利用一个有效的原位辐照NMR光谱方法,它是可能的,以确定在溶液中的两个DTE衍生物的光致变色开关能力,导致有关的结构,化学开环和闭合的DTE的平衡,以及这些分子开关的长期稳定性的关键信息。特别地,带有全氟化硫醚的化合物显示出显著的稳定性,几乎没有与DTE已知的不可逆环化副产物相关的疲劳。带有硫醚的DTE可以被脱保护并用于固定在金基底上,其特征在于在DTE官能化之前和之后通过水接触角测量。最后,通过循环伏安法研究了全氢DTE的电化学诱导开关能力,证明了其快速、定量和可逆的环化。我们设想这些材料作为传感器和光学开关器件的应用。
Photochromic compounds comprising small molecules and polymers have been shown to be of great interest in the field of stimuli-responsive materials for applications as sensors and (nano-) devices. In this regard dithienylethenes (DTEs) have been proven to be especially valuable because of their tolerance to chemicals and their good stability making them tunable and reversibly switchable between an open and a closed structure featuring different optical properties. By utilizing a potent in situ irradiation NMR spectroscopy approach, it is possible to determine the photochromic switching capability of two DTE derivatives in solution leading to crucial information about the structures, the equilibria of the chemical ring-opening and closing of the DTEs as well as the longtime stability of these molecular switches. In particular the perfluorinated thioether bearing compound shows remarkable stability with little fatigue related to the irreversibly cyclized byproduct known for DTEs. The thioether-bearing DTEs can be deprotected and used for immobilization on gold substrates which are characterized by water contact angle measurements prior to and after DTE functionalization. Finally, the electrochemically induced switching capability of the perhydro DTE is investigated by cyclic voltammetry proving its fast, quantitative and reversible cyclization. We envisage these materials for applications as sensors and optical switching devices.
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