Supramolecular Photoreactor

该项目重点关注基于二维超分子组装体的人工光合作用仿生方法。电荷转移（CT）配合物常被用作人工光合作用和光电导材料中的电荷分离装置。二维超分子组装体，例如双层膜和LB膜，是设计CT复合物的合适候选物。基于双层膜的“赝晶工程”，我们成功地在水双层膜中合成了一个由疏水性联苯和亲水性紫精分子头组成的分子间CT复合物，并将其与相邻分子的疏水性芳香链段紧密地结合在一起，形成了一个在460 nm处的宽吸收带，这是由于CT复合物的存在，C12 BphC 5V ~（2+）的水溶液在可见光区无吸收，而C8 BphC 10 V ~（2+）的水溶液在可见光区无吸收。在可见光照射下，还发现了一个长寿命的紫精自由基。通过聚离子络合物技术在ITO电极上制备的C12 BphC 5V 2+的Langmuir-Blodgett膜清楚地显示了紫精基团的可逆氧化还原反应，并且LB膜有效地介导了从电极到氧化还原黄素酶，心肌黄酶的电子。研究了黄递酶和NAD被光化学产生的紫精自由基的光化学还原。

This project focused a biomimetic approach of artificial photosynthesis based on two-dimensional supramolecular assemblies. Charge transfer (CT) complexes are often used as a charge separation device in an artificial photosynthesis and photo conductive materials. Two-dimensional supramolecular assemblies.e.g. bilayr membranes and Langmuir-Blodgett films, are suitable candidates for designing CT complexes. Based on "pseudo crystal engineering" of bilayr membranes, we succeeded tailoring an intermolecular CT complex between a hydrophobic biphenyl moiety and a hydrophilic viologen head in an aqueous bilayr membrane.The hydrophilic viologen head and the hydrophobic aromatic segment of the adjacent molecule was expected to be closely packed in the tilted molecular orientation.A broad absorption band at 460nm attributed to a CT complex was observed in the aqueous bilayr solution of C12BphC5V2+, whereas a water solution of C8BphC10V2+ had no absorption in visible region. A long lived viologen radicals was also found on visible light irradiation of the CT complex. Langmuir-Blodgett films of C12BphC5V2+ prepared by the polyion complex technique on ITO electrodes clearly showed reversible redox reaction of the Viologen group and the LB film effectively mediated electrons from the electrode to a redox flavin enzyme, diaphorase. Photochemical reduction of diaphorase and NAD by the photochemically generated viologen radical was investigated.