Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates†,Chemical Science

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Rapid photoinduced charge injection into covalent polyoxometalate–bodipy conjugates†
Chemical Science ( IF 7.6 ) Pub Date : 2018-06-01 00:00:00 , DOI: 10.1039/c8sc00862k
Fiona A Black ₁ , Aurélie Jacquart ₂ , Georgios Toupalas ₂ , Sandra Alves ₂ , Anna Proust ₂ , Ian P Clark ₃ , Elizabeth A Gibson ₁ , Guillaume Izzet ₂

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Controlled design of photoactive hybrids would provide highly active materials for solar energy conversion and photo(electro) catalysis. We describe the kinetics of photoinduced electron transfer in a series of photoactive hybrids based on Keggin-type polyoxometalates (POMs) covalently grafted to bodipy photosensitizers. We show how the electronic properties and corresponding dynamics of these hybrids can be readily tuned by varying the POM metal ion, the anchoring functionalization and the spacer length. Ultrafast visible and IR transient absorption spectroscopy, supported by spectroelectrochemical measurements, reveals that photoinduced electron transfer from the bodipy chromophore to the organosilyl POM derivative occurs as rapidly as τ = 54 ps to generate a long-lived (τ = 4.8 ns) charge-separated (CS) state, making this system appropriate for applications in photoelectrochemical devices.

中文翻译：

快速光致电荷注入共价多金属氧酸盐-bodipy缀合物†

光活性杂化物的受控设计将为太阳能转换和光（电）催化提供高活性材料。我们描述了一系列基于共价接枝到 bodipy 光敏剂的 Keggin 型多金属氧酸盐 (POM) 的光活性杂化物中光诱导电子转移的动力学。我们展示了如何通过改变 POM 金属离子、锚定官能化和间隔基长度来轻松调节这些杂化物的电子特性和相应的动力学。超快可见光和红外瞬态吸收光谱，在光谱电化学测量的支持下，揭示了从 bodipy 发色团到有机硅基 POM 衍生物的光诱导电子转移以τ = 54 ps 的速度发生，从而产生长寿命 ( τ = 4.8 ns) 的电荷分离（CS）状态，使得该系统适合在光电化学器件中的应用。

更新日期：2018-06-01

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