Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University , Beijing 100084, China.
ACS Appl Mater Interfaces. 2017 Jul 12;9(27):22635-22640. doi: 10.1021/acsami.7b07026. Epub 2017 Jun 26.
Visible-light photoinduced electron transfer (Vis-PET) is highly important for optoelectronic devices and photoredox catalysis. Herein, we propose a supramolecular strategy to promote the Vis-PET process by charge transfer (CT) interactions. As a proof of concept, a molecular system containing 1,5-alkoxy-substituted naphthalene and viologen moieties was designed to form a CT complex in water. The HOMO/LUMO energy gap was lowered by CT interaction, which turned on the Vis-PET process to generate viologen radical cations. Moreover, when CT interaction was enhanced by cucurbit[8]uril, the efficiency of the Vis-PET process was further promoted and the required irradiation wavelength could be further red-shifted by 100 nm. The Vis-PET system exhibited an improved activity of photocatalysis, as supported by the fast photoreduction of Cytochrome c. This study represents a facile supramolecular way to fabricate radicals with maintained activity under mild conditions, which holds potential to enrich the scope of visible-light photoredox catalysis by the rational utilization of CT systems.
可见光诱导电子转移(Vis-PET)对于光电设备和光还原催化非常重要。在此,我们提出了一种通过电荷转移(CT)相互作用促进 Vis-PET 过程的超分子策略。作为概念验证,设计了一个包含 1,5-烷氧基取代萘和紫罗碱部分的分子体系,以在水中形成 CT 配合物。CT 相互作用降低了 HOMO/LUMO 能隙,从而开启了 Vis-PET 过程,生成紫罗碱自由基阳离子。此外,当 CT 相互作用被葫芦[8]脲增强时,Vis-PET 过程的效率进一步提高,所需的辐照波长可以进一步红移 100nm。Vis-PET 体系表现出了更好的光催化活性,这得到了细胞色素 c 快速光还原的支持。该研究代表了一种在温和条件下保持自由基活性的简易超分子方法,通过合理利用 CT 体系,有可能丰富可见光光还原催化的范围。