Bioinspired Active Site with a Coordination-Adaptive Organosulfonate Ligand for Catalytic Water Oxidation at Neutral pH.
Bioinspired Active Site with a Coordination-Adaptive Organosulfonate Ligand for Catalytic Water Oxidation at Neutral pH.
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DOI：
10.1021/jacs.3c03415
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发表时间：
2023-05-31
影响因子：
15
通讯作者：
Sun, Licheng
中科院分区：
文献类型：
--
作者：
Liu, Tianqi;Zhan, Shaoqi;Shen, Nannan;Wang, Linqin;Szabo, Zoltan;Yang, Hao;Ahlquist, Marten S. G.;Sun, Licheng
许多酶使用适应性框架来预组织底物，适应中间体的各种结构和电子需求，并加速相关催化。受生物体系的启发，设计了一种含有构型不稳定配体[2，2 ′：6′，2 ″-三联吡啶]-6，6 ″-二磺酸盐的钌基分子水氧化催化剂，模拟酶的骨架结构，磺酸盐的配位高度灵活，既作为电子供体稳定高价钌，又作为质子受体加速水的解离，从而提高催化水氧化的性能.结合单晶X射线分析，不同温度的NMR，电化学技术，和DFT计算被用来调查的基本作用的自适应配体，表明按需的构型变化引起快速催化动力学的周转频率（TOF）超过2000 s-1，这是比较自然光合作用中的放氧复合物（OEC）。
Many enzymes use adaptive frameworks to preorganize substrates, accommodate various structural and electronic demands of intermediates, and accelerate related catalysis. Inspired by biological systems, a Ru-based molecular water oxidation catalyst containing a configurationally labile ligand [2,2′:6′,2″-terpyridine]-6,6″-disulfonate was designed to mimic enzymatic framework, in which the sulfonate coordination is highly flexible and functions as both an electron donor to stabilize high-valent Ru and a proton acceptor to accelerate water dissociation, thus boosting the catalytic water oxidation performance thermodynamically and kinetically. The combination of single-crystal X-ray analysis, various temperature NMR, electrochemical techniques, and DFT calculations was utilized to investigate the fundamental role of the self-adaptive ligand, demonstrating that the on-demand configurational changes give rise to fast catalytic kinetics with a turnover frequency (TOF) over 2000 s–1, which is compared to oxygen-evolving complex (OEC) in natural photosynthesis.
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