Light-induced water oxidation catalyzed by an oxido-bridged triruthenium complex with a Ru–O–Ru–O–Ru motif

Abstract

A μ-oxido-bridged triruthenium complex (RuT(2+)), formed by air-oxidation of a previously reported monoruthenium water oxidation catalyst (WOC), serves as an efficient photochemical WOC with the turnover frequency (TOF) and turnover number (TON) 0.90 s(-1) and 610, respectively. The crystal structures of RuT(2+) and its one-electron oxidized RuT(3+) are also reported.

Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru2Mn Complex

“…[1][2][3][4][5] During the past few decades, extraordinary efforts have been dedicated to the synthesis of manganese-based molecular complexes to mimic the structure and function of the OEC. [6][7][8][9][10] Other transition metals were also used for the synthesis of water oxidation catalysts, including Ru, [11][12][13][14][15][16][17][18][19][20][21][22][23][24] Ir, [25,26] Fe, [27][28][29][30][31] Co, [32][33][34] Ni, [35][36][37] and Cu. [38][39][40] Recently,the Llobet group disclosed the synthesisofaheterotrinuclear Ru 2 Mn complex A 0 {[Ru II (tpy)] 2 (m-[Mn II (bpp) 2 ]) (OAc) 2 } 2 + [tpy = 2,2':6',2''-terpyridine, bpp = 3,5-bis(2-pyridyl)pyrazolate].…”

Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization

“…Currently there are many mono-Ru [4][5][6][7] and di-Ru [8][9][10][11] complexes capable of oxidizing water; however, the stability of molecular catalysts in highly oxidizing conditions is still a major issue, with most known catalysts deactivating after some time [12]. Under strongly oxidizing conditions one of the reaction pathways for single-site complexes involves the formation of dinuclear complexes [13][14][15]. In some cases, the dinuclear complexes are more stable than their mononuclear counterparts, with the mononuclear catalyst being converted to a binuclear or multinuclear catalyst [13,15].…”

“…Under strongly oxidizing conditions one of the reaction pathways for single-site complexes involves the formation of dinuclear complexes [13][14][15]. In some cases, the dinuclear complexes are more stable than their mononuclear counterparts, with the mononuclear catalyst being converted to a binuclear or multinuclear catalyst [13,15].…”

Vertical Step‐Growth Polymerization Driven by Electrochemical Stimuli from an Electrode

“…As the number of Ru units increased with respect to SAM (CzP(Ru) n , n = 0), the absorbance and current intensity of CzP(Ru) n increased regularly and exhibited ag ood linear relationship with the switching time between alternating potentials (Figures 1a nd 2a). [20] We analyzed the molecular wire by mass spectrometry after treatment with HF,b ut no evidence of molecular fragments was obtained, probably owing to the detection limit of trace molecules.C Vs were measured in aqueous solution instead of acetonitrile so that the redox peaks could be observed better.After n increased to 9, further polymerization was difficult (Figure 1a), probably because the length of CzP(Ru) 9 had reached the width of the electric double layer, which is generally considered to have am aximum value of 20 nm. [20] We analyzed the molecular wire by mass spectrometry after treatment with HF,b ut no evidence of molecular fragments was obtained, probably owing to the detection limit of trace molecules.C Vs were measured in aqueous solution instead of acetonitrile so that the redox peaks could be observed better.After n increased to 9, further polymerization was difficult (Figure 1a), probably because the length of CzP(Ru) 9 had reached the width of the electric double layer, which is generally considered to have am aximum value of 20 nm.…”