Department of Chemistry, School of Engineering Sciences in, Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10044, Stockholm, Sweden.
Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10691, Stockholm, Sweden.
Chemistry. 2022 Apr 27;28(24):e202104562. doi: 10.1002/chem.202104562. Epub 2022 Mar 24.
The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man-made molecular catalysts. Herein, four Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) based molecular water oxidation catalysts with well-defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high-valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6-fold rate increase for water oxidation catalysis has been achieved.
金属酶的外配位球在其高催化活性中经常起着重要作用，但在人为设计分子催化剂时，这一原则很少被考虑。在此，设计并合成了四个具有明确外球的基于 Ru-bda（bda=2,2'-联吡啶-6,6'-二羧酸）的分子水氧化催化剂。实验和理论研究表明，Ru 中心周围的疏水环境可以导致高价中间体的热力学稳定，并在催化水氧化过程中加速质子转移过程。通过这种外球稳定作用，水氧化催化的速率提高了 6 倍。
