Visible‐Light‐Driven Generation of High‐Valent Oxo‐Bridged Dinuclear and Tetranuclear Manganese Terpyridine Entities Linked to Photoactive Ruthenium Units of Relevance to Photosystem II

Abstract

International audienc

Alternated bimetallic [Ru–M] (M = Fe2+, Zn2+) coordination polymers based on [Ru(bpy)3]2+ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

“…[{Ru II (bpyc À ) 2 (tpyc À -bpy-tpyc À )Fe II } n ] 0 (eqn (5)), inducing their strong adsorption (aer precipitation) on the electrode surface. It should be noted that such an electrodeposition phenomenon was not observed for the trinuclear complexes [{Ru II (bpy) 2 L1} 2 M] n+ (M ¼ Fe 2+ , Zn 2+ , Co 2+ , Co 3+ and Mn 2+ ) [27][28][29][30][31] by similar reductive scanning. This conrms unambiguously the macromolecular nature of the in situ formed species.…”

“…We previously reported the synthesis of one of the rare examples of heteroditopic ligands containing one 2,2 0 -bipyridine and one or two 2,2 0 :6 0 ,2 00 -terpyridyl moieties and their Ru(II) tris(bipyridine)-like complexes [Ru(bpy) 2 (L1)] 2+ and [Ru(bpy) 2 (L2)] 2+ , respectively (Scheme 1). 26 We also prepared the corresponding heterobimetallic trinuclear complexes [M {Ru II (bpy) 2 (L1)} 2 ] n+ with M ¼ Fe 2+ , Zn 2+ , Co 2+ , Co 3+ and Mn 2+ of the single terpyridyl derivative A [27][28][29][30][31] and fully studied their redox and photophysical behaviours, as well as their capabilities to photoinduce redox reactions in solution.…”

Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges

“…The oxidized photosensitizer subsequently abstracts an electron from the attached Mn complex. [87][88][89][90][91][92] Of the examined Ru-Mn assemblies, assembly 16 ( Fig. 8) displayed promising properties as it was able to undergo three consecutive electron transfers, which converted the initial Mn II,II 2 core to Mn III,IV 2 .…”

Enhanced Photoinduced Electron Transfer Through a Tyrosine Relay in a De Novo Designed Protein Scaffold Bearing a Photoredox Unit and a FeIIS4 Site

“…[4] Synthetic chemists too have sought to incorporate relays into biomimetic molecular systems [10][11][12][13][14][15][16][17] as well as in catalytic systems. [18][19][20][21][22] While electron transfer has been examined by protein design, [23,24] the design of electron relays such as those found in PSII and RNR has been less studied. Not only does protein design offer the opportunity to examine the fundamental requirements for function in electron transfer relays, but the implementation of these principles into extant systems may provide new tools for improving the interfacing between grafted catalytic modules and the electrode or for providing directional electron transfer processes in artificial photosynthetic systems.…”

“…Electron transfer relays have long been studied in proteins and protein assemblies such as Photosystem II (PSII) and ribonucleotide reductase (RNR) to understand these processes in their native context [4] . Synthetic chemists too have sought to incorporate relays into biomimetic molecular systems [10–17] as well as in catalytic systems [18–22] . While electron transfer has been examined by protein design, [23,24] the design of electron relays such as those found in PSII and RNR has been less studied.…”