含光敏剂卟啉大环的DuBois配合物的设计合成及催化产氢研究

This project will try to synthesize the hitherto unknown light-driven type of Dubois complexes by connecting the photosensitive porphyrin macrocycles to the molecular skeletons of Dubois complexes. According to our designed synthetic route, two classes of light-driven Dubois complexes can be prepared, in which the porphyrin macrocycles are attached to the P or N atoms located in molecular skeletons of Dubois complexes, respectively. On the basis of synthesis and structural characterization of these two classes of light-driven complexes, we will systematically study the photoinduced H2 production from water catalyzed by these two classes of complexes and reveal the inherent relationship between the structures and the H2-producing function of such two classes of light-driven complexes. Apparently, the revealed relationship will be helpful to development of the highly efficient light-driven Dubois catalysts for production of green and renewable H2 fuel. This project is of theoretical and practical significance and will promote the development of organometallic chemistry, hydrogenase bionics, catalysis, energy source and material science.

本项目拟将光敏剂卟啉大环导入DuBois型配合物的分子骨架上，以构成至今尚未见报道的光驱动型DuBois配合物。按照我们所设计的合成路线可制备两类光驱动型DuBois配合物，一类是光敏剂卟啉连在DuBois配合物分子骨架的P原子上，另一类是连在DuBois配合物分子骨架的N原子上。本项目将在合成和确定这两类配合物结构的基础上，系统深入地研究它们在可见光驱动下催化水中质子还原为氢气的能力，并揭示结构与催化功能之间的关系，为进一步研发利用太阳能和水生产绿色可再生燃料H2气的高效催化剂提供科学依据。本项目对促进金属有机化学、氢化酶仿生学、催化及能源材料等多种学科的发展，具有重要理论和实际意义。

本项目设计合成了含 DuBois 双膦双氮配体的双核镍配合物和含卟啉大环双膦双氮 (P2N2) 或单膦双氮 (PN2) 配体的 DuBois 配合物，用现代物理化学方法充分表征了它们的结构。研究了某些代表性化合物的电化学及光化学性质，发现它们具有良好的电催化及光诱导催化质子还原为氢气的功能, 取得了创新性研究成果。本项目对促进金属有机化学、催化及能源材料等多种学科的发展，具有重要理论和实际意义。