Abstract：
Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal-coordination-driven self-assembly, we report the preparation of a series of isoreticular tetraphenylethylene-based metallacages, which are well characterized by multinuclear NMR, ESI-TOF-MS and single-crystal X-ray diffraction techniques. The suitable integration of photosensitizing tetraphenylethylene units as faces and Re catalytic complexes as the pillars into a single metallacage offers a high photocatalytic hydrogen production rate of 1707 μmol g-1 h-1 , which is one of the highest values among reported metallacages. Femtosecond transient absorption and DFT calculations reveal that the metallacage can serve as a platform for the precise and organized arrangement of the two building blocks, enabling efficient and directional electron transfer for highly efficient photocatalytic performance. This study provides a general strategy to integrate multifunctional ligands into a certain metallacage to improve the efficiency of photocatalytic hydrogen production, which will guide the future design of metallacages towards photocatalysis.
摘要：
多组分金属可以集成其不同构建块的功能，以实现高级应用的协同效应。在这里，基于金属配位驱动的自组装，我们报告了一系列等网状四苯基乙烯基金属陶瓷的制备，多核核磁共振有很好的特征，ESI-TOF-MS和单晶X射线衍射技术。将光敏四苯基乙烯单元作为面和Re催化络合物作为支柱适当地整合到单个金属陶瓷中，可提供1707μmolg-1h-1的高光催化制氢速率，这是报道的金属陶瓷中的最高值之一。飞秒瞬态吸收和DFT计算表明，金属层可以作为两个构建块的精确和有组织排列的平台，使高效和定向电子转移高效的光催化性能。本研究提供了将多功能配体整合到一定的金属化合物中以提高光催化制氢效率的一般策略，这将指导未来的金属陶瓷设计走向光催化。
