Visible-Light-Driven "On"/"Off" Photochromism of a Polyoxometalate Diarylethene Coordination Complex.
Visible-Light-Driven "On"/"Off" Photochromism of a Polyoxometalate Diarylethene Coordination Complex.
复制标题
DOI：
10.1021/jacs.8b04900
复制
发表时间：
2018-07
影响因子：
15
通讯作者：
Jingjing Xu;Henrieta Volfová;R. Mulder;L. Goerigk;G. Bryant;E. Riedle;C. Ritchie
中科院分区：
文献类型：
--
作者：
Jingjing Xu;Henrieta Volfová;R. Mulder;L. Goerigk;G. Bryant;E. Riedle;C. Ritchie
本文报道了第一个基于光致变色聚氧乙烯酸盐（POM）的二芳基乙烯（DAE）配位化合物，该化合物是通过将两个钴（III）掺杂的硼钨酸盐[BIIIWVI 11 O39 CoIII]6-与双配位的含吡啶基的二芳基乙烯（C25 H16 N2 F6 S2）连接而制备的。利用1H和19 F核磁共振谱（NMR）、电喷雾电离四极飞行时间质谱（ESI-MS）和质谱（MS）对组装体的溶液状态组成、结构和稳定性进行了研究。（ESI-QTOF-MS）、紫外-可见光谱（UV-vis）和小角X射线散射（SAXS），揭示了由于静电和空间的考虑，该复合物自组织成采用分子哑铃结构。这种构象是光环化反应的先决条件。组装被发现是可切换的两个状态之间使用可见光由于扰动的DAE电子结构上的协调POM。我们目前的物理数据，包括在两个方向上的分子开关的反应量子效率测量使用定制的量子产率测定设置，除了在长时间照射的抗疲劳性。
Herein we report the first photochromic polyoxometalate (POM)-based diarylethene (DAE) coordination complex, prepared by ligation of two cobalt(III)-incorporated borotungstates [BIIIWVI11O39CoIII]6- with the ditopic pyridyl-containing diarylethene (C25H16N2F6S2). The solution-state composition, structure, and stability of the assembly were probed using 1H and 19F nuclear magnetic resonance spectroscopy (NMR), electrospray ionization quadrupolar time-of-flight mass spectrometry (ESI-QTOF-MS), ultraviolet-visible spectroscopy (UV-vis), and small-angle X-ray scattering (SAXS), revealing that the complex self-organizes to adopt a molecular dumbbell structure due to electrostatic and steric considerations. This conformation is a prerequisite for the photocyclization reaction. The assembly was found to be switchable between two states using visible light due to the perturbation of the DAE electronic structure on coordination to the POM. We present photophysical data, including the reaction quantum efficiency of the molecular switch in both directions measured using a custom-built quantum yield determination setup in addition to fatigue resistance on prolonged irradiation.