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The Supramolecular Redox Functions of Metallomacromolecules Didier Astruc

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The Supramolecular Redox Functions of Metallomacromolecules Didier Astruc Astruc Journal of Leather Science and Engineering (2020) 2:13 Journal of Leather Science https://doi.org/10.1186/s42825-020-00026-z and Engineering REVIEW Open Access The supramolecular redox functions of metallomacromolecules Didier Astruc Abstract Metallomacromolecules are frequently encountered in redox proteins including metal-tanned hide collagen and play crucial roles involving supramolecular properties in biological electron-transfer processes. They are also currently found in non-natural families, such as: metallopolymers, metallodendrimers and metallodendronic polymers. This mini-review discusses the supramolecular redox functions of such nanomaterials developed in our research group. Electron-transfer processes are first examined in mono-, bis- and hexa-nuclear ferrocenes and other electron-reservoir organoiron systems showing the influence of supramolecular and reorganization aspects on their mechanism. Then applications of electron-transfer processes using these same organoiron redox systems in metallomacromolecules and their supramolecular functions are discussed including redox recognition/sensing, catalysis templates, electrocatalysis, redox catalysis, molecular machines, electrochromes, drug delivery device and nanobatteries. Keywords: Ferrocene, electron reservoir, Polymer, Dendrimer, Redox catalyst, Redox sensor, Molecular machine, Supramolecular template, Electrochrome, Drug delivery device, Battery 1 Introduction pigments, clusters found in ferredoxins and other metal- The supramolecular redox functions of metallomacro- locyclic nitrogen ligands such as corrolle found in vita- molecules are ubiquitous in the chemistry of life [1]as min B12 [1]. Interestingly non-biological redox reagent exemplified by electron transfers in metalloproteins [2], using metals and ligands that are not found in living sys- the role of ferredoxins achieving electron transfers in tem can also achieve remarkable performances, such as many redox reactions of the metabolism including polypyridyl-noble metal complexes that are useful in photosynthesis [3] and nitrogenase [4], and a number of photophysical processes, organic synthesis [12] and other biocatalytic redox processes of metalloenzymes polyphenol-metal (e.g. AlIII,CrIII) complexes that are [5]. Nature has also inspired chemists for the mimicry of powerful tanning system to improve the hydrothermal biological redox processes in modern technology, for in- stability of tanned leather [9]. Another well-known and stance in the fields of energy [6, 7], nanomedicine [8], current family of non-natural redox systems that could and the metal-tanning process of leather industry [9]. be rationalized and optimized regarding its usefulness is The designs of redox reagents mimicking the redox sites that of the late transition-metal sandwich complexes of metalloenzymes range from metalloporphyrins [10] [13]. This later area has concentrated our attention dur- that are found as redox site of oxidoreductase enzymes ing several decades and will be discussed in this mini- such cytochromes that are involved in many crucial review essentially based on research conducted in our la- functions, metallophthalocyanins [11] found in boratories. When these non-natural redox systems are engaged in macromolecular materials, their redox switch Correspondence: [email protected] can exert a variety of functions and processes that are Dedicated to our distinguished colleague and friend Professor Wuyong Chen used in synthesis, catalysis, biomedicine and materials (University of Sichuan, Chengdu) at the occasion of his 68th birthday. ISM, UMR CNRS 5255, Univ. Bordeaux, 351 Cours de la Libération, 33405 science [14]. In biological as well as non-natural pro- Talence Cedex, France cesses, the supramolecular aspects involving the redox © The Author(s). 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Astruc Journal of Leather Science and Engineering (2020) 2:13 Page 2 of 17 centers and their close ligand environment play a par- inorganic substrates, demonstrating the remarkable use- ticularly crucial role due to the hydrogen bonds, elec- fulness of this new family of complexes that were called trostatic interaction and redox-induced structural and “Electron Reservoirs” [28–32]. 5 conformational changes in these metallomacromole- The Cp* series (Cp* = η -C5Me5) are also known in cules [15]. both families of complexes and present even more ro- bust redox systems as electron reservoirs [17, 21, 23, 29, 2 Electron transfer by Electron-rich Organo-Iron 33] that have been integrated in polymers and dendri- Sandwich complexes mers (see text). The stabilities of the redox states of a redox reagent Neutral Fe(I) sandwich complexes, such as CpFeI(η6- I 6 5 within a given timescale are a fundamental criterium to- C6Me6), I, and Cp*Fe (η -C6Me6) in which Cp = η -C5H5 5 ward functions. This story started with the discovery of and Cp* = η -C5Me5 [33] that are Jahn-Teller active [34] ferrocene in the late 1940’s and early 1950’s, mainly by have indeed been found by He(I) photoelectron spec- Fischer, Wilkinson and Woodward [16], that boosted a troscopy to be the most electron-rich known neutral number of disciplines including organotransition-metal molecules and remain so to-date based on the extremely chemistry, homogeneous catalysis and materials science low values of their ionization potentials [35]. These com- [17]. In the early days of organotransition-metal chemis- plexes are excellent initiators of electron-transfer-chain try, research on single electron-transfer aspects and their reactions [36, 37] and redox catalysts for the reduction subsequent chemistry was not privileged besides electro- of nitrate and nitrites to ammonia [38, 39]. Interestingly, chemical studies [18, 19]. In the early days, redox they react very fast with O2 or air even under sub- changes were found to be central in transition-metal ambient conditions. For instance, the forest-green proto- chemistry, however, as illustrated by Taube when he type complex I provides an extremely mild C-H activa- classified ligand-substitution reactions as a function of tion upon such a simple contact with O2 yielding the the metal oxidation state [20, 21]. In ferrocene chemis- red ferrocene-like cyclohexadienylidene Fe (II) deriva- try, the oxidation of the parent ferrocene and its alkyl- tive. The superoxide radical anion was detected by its substituted derivatives is straightforward in a region of characteristic EPR spectrum as a reaction intermediate. potentials that are readily accessible with a large choice Its formation is due to fast exergonic electron transfer + of oxidizing reagents and at a convenient oxidation po- from Fe(I) to O2 leading to a contact ion pair [Fe(II) , .- tential around + 0.4 V vs. saturated calomel electrode O2 ] in which benzylic deprotonation by superoxide (SCE) in organic solvents such as THF, 1,2-dichloro- anion activated by the positive charge on the sandwich methane, and acetonitrile [22]. Under these conditions, compound is also fast even at very low temperature. The the isolation of the oxidized form of ferrocene, ferrice- nucleophilic reactivity of the cyclohexadienylidene com- nium (a d5 Fe(III), 17-electron complex), is relatively plex is very rich and useful, forming a variety of bonds − easy using tetrafluoroborate (BF4 ) or hexafluoropho- upon reactions with many electrophiles [39, 40]. The − 6 x+ sphate (PF6 ) as a counter-anion. In turn, the latter salts complexes [C5R5Fe(η -C6Me6)] were isolated in the can be used as mild single-electron oxidants [23]. Due to three oxidation states (x = 0–2) corresponding to Fe(II,I, the absence of an electron in a bonding orbital [24] 0), and electron-transfer interplay involving various and the positive charge, however, this cation is some- substrates were demonstrated [41]. In addition, the what fragile in solution especially in polar solvents, structure-reactivity relationships, established with the 6 and the situation becomes even more complicated family of mixed sandwich complexes C5R5Fe(η -C6Me6), when a ferrocene ring bears an electron-withdrawing R = H or Me, have been generalized to first-row late substituent such as an acyl group due to the anodic transition metal sandwich complexes for which the neu- shift of the redox potential and the decreased stability tral forms have 19- or 20 valence electrons, as for in- of the oxidized form [25]. On the cathodic side, re- stance to the 19-electron cobaltocene derivatives [(η5- 5 duction of ferrocene itself has been observed by cyclic C5R5)Co(η -C5R’5)] (R, R’ = H or Me) [42] and the 20- 6 voltammetry, but the cathodic potential is so negative electron complex [Fe(η -C6Me6)2,[43]]. Even main (− 3Vvs.SCE)thattheisolationoftheferrocene
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