Yamazaki Yasuomi, Ishitani Osamu
Department of Chemistry , Graduate School of Science and Engineering , Tokyo Institute of Technology , 2-12-1-NE-1 Ookayama, Meguro-ku , Tokyo , 152-8550 , Japan . Email:
Chem Sci. 2017 Dec 4;9(4):1031-1041. doi: 10.1039/c7sc04162d. eCollection 2018 Jan 28.
Photofunctional trinuclear complexes containing three different central metals, Os(ii), Re(i) and Ru(ii), were synthesised for the first time using stepwise Mizoroki-Heck reactions. The vinylene groups in the bridging ligands of the Os(ii)-Re(i)-Ru(ii) trinuclear complexes were selectively reduced by photochemical hydrogenation in moderate yield, affording novel supramolecular photocatalysts which can absorb a wide range of visible light up to 730 nm and induce CO reduction with high selectivity and durability. The turnover numbers of CO formation were over 4300. Details of the photophysical properties of these new trinuclear complexes, especially their intramolecular excitation-energy transfer phenomena, are also reported.
首次通过逐步的 Mizoroki-Heck 反应合成了包含三种不同中心金属(Os(ii)、Re(i) 和 Ru(ii))的光功能三核配合物。Os(ii)-Re(i)-Ru(ii) 三核配合物桥连配体中的亚乙烯基通过光化学氢化反应被选择性还原,产率适中,得到了新型超分子光催化剂,该催化剂能够吸收高达 730 nm 的宽范围可见光,并以高选择性和耐久性诱导 CO 还原。CO 生成的周转数超过 4300。还报道了这些新型三核配合物的光物理性质细节,特别是它们的分子内激发能转移现象。