A Calix[4]arene‐Based Cyclic Dinuclear Ruthenium Complex for Light‐Driven Catalytic Water Oxidation,Chemistry - A European Journal

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A Calix[4]arene‐Based Cyclic Dinuclear Ruthenium Complex for Light‐Driven Catalytic Water Oxidation
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-11-26 , DOI: 10.1002/chem.202004486
Niklas Noll ₁ , Frank Würthner _{1,

2}

Affiliation

A cyclic dinuclear ruthenium(bda) (bda: 2,2’‐bipyridine‐6,6’‐dicarboxylate) complex equipped with oligo(ethylene glycol)‐functionalized axial calix[4]arene ligands has been synthesized for homogenous catalytic water oxidation. This novel Ru(bda) macrocycle showed significantly increased catalytic activity in chemical and photocatalytic water oxidation compared to the archetype mononuclear reference [Ru(bda)(pic)₂]. Kinetic investigations, including kinetic isotope effect studies, disclosed a unimolecular water nucleophilic attack mechanism of this novel dinuclear water oxidation catalyst (WOC) under the involvement of the second coordination sphere. Photocatalytic water oxidation with this cyclic dinuclear Ru complex using [Ru(bpy)₃]Cl₂ as a standard photosensitizer revealed a turnover frequency of 15.5 s⁻¹ and a turnover number of 460. This so far highest photocatalytic performance reported for a Ru(bda) complex underlines the potential of this water‐soluble WOC for artificial photosynthesis.

中文翻译：

用于光驱动催化水氧化的杯[4]芳烃基环状双核钌配合物

合成了一种配备有低聚（乙二醇）功能化轴向杯[4]芳烃配体的环状双核钌（bda）（bda：2,2'-联吡啶-6,6'-二羧酸酯）络合物，用于均相催化水氧化。与原型单核参考[Ru(bda)(pic) ₂ ]相比，这种新型Ru(bda)大环在化学和光催化水氧化方面表现出显着增加的催化活性。动力学研究，包括动力学同位素效应研究，揭示了这种新型双核水氧化催化剂（WOC）在第二配位层参与下的单分子水亲核攻击机制。使用 [Ru(bpy) ₃ ]Cl ₂作为标准光敏剂，用这种环状双核 Ru 络合物进行光催化水氧化，结果显示周转频率为 15.5 s ^-1 ，周转数为 460。这是迄今为止报道的 Ru( bda) 复合物强调了这种水溶性 WOC 在人工光合作用方面的潜力。

更新日期：2021-01-04

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