Multifunctional bi-redox radical organic molecules

Abstract

The invention relates to bipolar bi-redox-active compounds of general formula (I). The invention also relates to specific applications of these compounds associated with their electrochemical properties.

Description

[0001] DESCRIPTION

[0002] TITLE: MULTIFUNCTIONAL BI-REDOX RADICAL ORGANIC MOLECULES

[0003] FIELD OF INVENTION

[0004] The invention relates to a family of bipolar bi-redox organic radical molecules miscible in polar liquids and exhibiting electronic conductor properties. Molecules in this family can have various functional groups, making it possible to obtain ionic liquids, zwitterionic molecules, polymerizable and / or charged molecules, for a wide range of applications, particularly electrochemical and bioelectrochemical.

[0005] STATE OF THE ART

[0006] Environmental concerns and increasing energy demand are making the need for energy storage solutions increasingly urgent. Similarly, wireless systems and new technologies for connected devices are contributing to this growing need for human activity. This need is further reinforced by the increasing share of renewable energy sources (wind, solar, and even hydroelectric) in electricity consumption, the production of which is inherently unpredictable and inconsistent.

[0007] Among storage devices, we also know of flexible solid-state microbatteries and supercapacitors which are considered next-generation energy storage systems due to their power and energy density characteristics, good stability, safety of use, ability to adapt to different substrates and the possibility of producing them on a large scale.

[0008] Redox flow batteries (RFBs), which decouple power and energy capacity, are also well-known; they represent a promising large-scale energy storage solution for regulating and supporting intermittent renewable energy sources. RFBs are experiencing massive development thanks to the use of electroactive organic materials. Their high theoretical capacity, the abundance of these materials, and the diversity of modular structures make them preferable to their inorganic counterparts. For example, the design of an aqueous redox-flow cell using organic compounds (viologen / nitroxide) with reduced viscosity and limited corrosivity has been described (WO2017025177).

[0009] Indeed, conventional energy storage system technologies often involve the use of various critical metals or heavy metals, which is undesirable according to current sustainability or environmental standards.

[0010] The shift in energy paradigms towards low-carbon and more sustainable societies necessitates the development of new materials with simple synthesis processes that use few, if any, critical resources, and involve few steps and minimal inputs. The use of exclusively organic materials opens the door to sustainable energy storage solutions. Furthermore, using materials of the same nature for both the anode and cathode could facilitate the recycling of these energy storage devices.

[0011] Bipolar redox-active organic molecules, also called bi-redox molecules, thus appear as suitable candidates for electroactive materials for electrochemical energy storage. Due to their multiple redox states, these bi-redox molecules can be deployed as positive (cathodes) and negative (anodes) materials in batteries such as solid-state batteries or RFBs. These bi-redox materials enable the use of the symmetrical battery concept, that is, a battery using the same material at both the anode and cathode. In addition to the aforementioned environmental benefits, these batteries are particularly simple to design and avoid cross-contamination problems (as seen in RFBs, for example).

[0012] However, these materials often exhibit unsatisfactory solubility and stability.

[0013] There is therefore a growing need for molecules / materials suitable for use in batteries, particularly symmetrical ones, with improved solubility and stability, enabling us to meet new standards and the growing need for sustainable energy storage.

[0014] The inventors have identified a new family of bi-redox molecules, derived from the radical (2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl or TEMPO, which meet the above requirements and whose synthesis processes are simple, rapid, and do not use critical materials. BRIEF SUMMARY OF THE INVENTION

[0015] Thus, a first object of the invention relates to a bipolar bi-redox-active compound of general formula (I)

[0016] (O in which:

[0017] A is selected from: o an amino alkyl of formula , where R is selected from a hydrogen atom or an alkyl group in (C1-C5), and n is between 1 and 5; in this case, advantageously A contributes acid-base properties due to the electron pair of the nitrogen atom; preferably, the nitrogen is bonded to group B; or an amino alkyl imidazolium of formula where R is selected from a hydrogen atom or an (C1-C5) alkyl, and n and m are independently between 1 and 5; in this case, advantageously A brings acid-base property due to the nitrogen of the electron pair of the nitrogen atom and ionic liquid due to the imidazolium; or o an (C1-C5) alkyl, preferably it will be linked to a viologenic type B group, the B group itself being able to be linked to a C group described below;

[0018] B is an electron acceptor group, selected from a viologen, anthraquinone, or quinone type group,

[0019] C is an optional group, for example an electron donor, selected from: o a polymerizable function which is a C2-C6 α-olefin, with the formula: between 1 and 4; or a group of officers selected from

[0020] -OOC allowing the realization of a zwitterion; or an electron-donating group selected from the group of formula II in which R is selected from a hydrogen atom or an alkyl group in the Ci-Cs group, and n is between 1 and 5. This group advantageously exhibits an acid-base function due to the nitrogen on the amino alkyl portion. These compounds are particularly stable and exhibit exceptionally high electrochemical performance.

[0021] It is specified that, in this description, the indices n and m relating to the different groupings are defined for each specific group and that their value, as well as the scope of their definition, may vary from one grouping to another. Furthermore, when indices n and m are present on the same grouping, their value may be chosen independently. Alternatively, n and m may take the same value.

[0022] One object of the invention relates to a bipolar bi-redox-active compound of general formula (I) in which:

[0023] A is selected from: o an amino alkyl of formula , where R is selected from a hydrogen atom or an alkyl group in (C1-C5), and n is between 1 and 5; in this case, advantageously A contributes an acid-base property due to the electron pair of the nitrogen atom; preferably, the nitrogen is bonded to group B; or o an amino alkyl imidazolium of formula R is selected from a hydrogen atom or an alkyl group in (C1-C5), and n is between 1 and 5; in this case, advantageously A provides acid-base properties due to the nitrogen electron pair of the nitrogen atom and ionic liquid properties due to the imidazolium; or o an alkyl group in (C1-C5), preferably it will be linked to a viologenic type group B, the group B itself being able to be linked to a group C described below,

[0024] B is an electron acceptor group, selected from a viologen, anthraquinone, or quinone type group,

[0025] C is an optional group, for example an electron donor, selected from: o a polymerizable function which is a C2-C6 α-olefin, with the formula: between 1 and 4; or a group of officers selected from

[0026] -OOC allowing the realization of a zwitterion; or an electron-donating group selected from the group of formula II in which R is selected from a hydrogen atom or an alkyl in Ci-Cs and n is between 1 and 5. This group exhibits an acid-base function due to the nitrogen on the amino alkyl part.

[0027] According to other optional features of the bipolar bi-redox-active compound according to the invention, the latter may include one or more of the following features, alone or in combination: the electron acceptor group B is of the viologenic type;

[0028] C is selected from: the polymerizable function which is a C2-C6 α-olefin, of formula the electron acceptor group B which is a quinone-type group or an anthraquinone of formula group B is a quinone or anthraquinone type group, group A is an aminoalkyl or amino alkyl imidiazolium, and a group C is present.

[0029] C is the electron-donating group with formula II in which R is selected from a hydrogen atom or an alkyl in Ci-Cs and n is between 1 and 5;

[0030] The bipolar bi-redox-active compound has the formula Hla or 111 b: with R selected from a hydrogen atom or an alkyl in (C1-C5), and n between 1 and 5; said bipolar bi-redox-active compound being of formula Ilia or II Ib: with R selected from a hydrogen atom or an alkyl group in (C1-C5), and n and m are independently between 1 and 5. - The bipolar bi-redox-active compound according to the invention, of formula IVa or IVb:

[0031] (IVb), with n between 1 and 5;

[0032] The bipolar bi-redox-active compound according to the invention, of formula V:

[0033] (V), with m between 1 and 4 and n between 1 and 5; - The bipolar bi-redox-active compound according to the invention, of formula Via or Vlb:

[0034] (Vlb), with R selected from a hydrogen atom or an alkyl in (C1-C5), and n between 1 and 5; said bipolar bi-redox-active compound having the formula Via or Vlb:

[0035] (Vlb), with R selected from a hydrogen atom or an alkyl in (C1-C5), and n and m are independently between 1 and 5.

[0036] The bipolar bi-redox-active compound according to the invention, of formula Vila or VII b:

[0037] (Vllb), with R selected from a hydrogen atom or an alkyl in (C1-C5), and n between 1 and 5; said bipolar bi-redox-active compound being formula Vila or VI I b:

[0038] (Vllb), with R selected from a hydrogen atom or an alkyl group in (C1-C5), and n and m are independently between 1 and 5. The bipolar bi-redox-active compound of formula I is chosen from the following compounds (table):

[0039] [Table 1] when a quaternary amine is present, its counter anion is selected from: Br, Cl', I', , or mixtures thereof.

[0040] When the bipolar redox-active compound is charged, a counter anion is selected from:

[0041] Br, CI-, I', , or mixtures thereof.

[0042] As mentioned, bipolar redox-active compounds according to formula I are characterized by being miscible in a polar solvent, which is of particular interest in the field of electrochemistry.

[0043] According to a second object, the invention relates to the use of a bipolar redox-active compound according to the invention as an electronic conductor or electronic relay for the transfer of electrons in redox systems such as energy storage systems for example a supercapacitor, a solid battery, a redox flow battery, a symmetric battery, and catalytic systems.

[0044] According to a third object, the invention relates to an electrochemical system comprising at least one bi-redox-active bipolar compound according to the invention.

[0045] According to other optional features of the electrochemical system according to the third object of the invention: said at least one bipolar bi-redox-active compound is immobilized for example by printing methods (additive manufacturing) at the cathode and / or immobilized for example by printing methods (additive manufacturing) at the anode, and / or is in solution, said at least one bipolar bi-redox-active compound is immobilized for example by printing methods (additive manufacturing) the anode and the cathode, the anode and the cathode comprise the same redox-active compound according to the invention immobilized for example by printing methods (additive manufacturing).

[0046] According to a fourth object, the invention relates to an energy storage device such as a supercapacitor, a solid-state battery, a redox flow battery, a symmetric battery comprising the electrochemical system according to the third object of the invention.

[0047] According to optional features of the energy storage device according to the invention, the device is an electrochromic device such as an electrochromic battery, comprising an electrochemical system including at least one bi-redox-active bipolar compound according to the invention immobilized at at least one of its electrodes.

[0048] The inventors have developed synthetic processes comprising a small number of steps and economical in scarce resources to synthesize the bi-redox-active bipolar compounds of formula I of the invention.

[0049] According to a fifth object, the invention relates to a method for synthesizing a bipolar redox-active compound according to the invention of formula Ilia or II Ib: according to the following summary diagram: step A) in which,

[0050] ACN is acetonitrile

[0051] DCM is dichloromethyl,

[0052] - L <n<5,

[0053] - 40 <X<60 - R est sélectionné parmi est sélectionné parmi un atome d'hydrogène ou un alkyl en (C1-C5). Selon un sixième objet, l'invention concerne un procédé de synthèse d'un composé bi-redox- actif bipolaire selon l'invention de formule IVa : according to the following reaction scheme: step A) step C)

[0054] IVa and in which

[0055] ACN is acetonitrile - DCM is dichloromethyl,

[0056] DMF is N,N-dimethylformamide

[0057] - L <n<5.

[0058] According to a seventh object, the invention relates to a method for synthesizing a bipolar redox-active compound according to the invention of formula IVb: according to the following reaction scheme: - step A) step B) and in which - ACN is acetonitrile,

[0059] DCM is dichloromethyl,

[0060] DMF is N,N-dimethylformamide.

[0061] - L <n<5. Selon un huitième objet, l'invention concerne un procédé de synthèse d'un composé bi- redox-actif bipolaire selon l'invention de formule (V):

[0062] according to the following reaction scheme: step A)

[0063] and in which

[0064] ACN is acetonitrile - DCM is dichloromethyl,

[0065] DMF is N,N-dimethylformamide

[0066] - L <n<5,

[0067] - L <m<4. Selon un neuvième objet, l'invention concerne un procédé de synthèse d'un composé bi- redox-actif bipolaire selon l'invention de formule Via: according to the following reaction scheme: - step A) step B) and in which

[0068] DCM is dichloromethyl,

[0069] - L <n<5.

[0070] According to a tenth object, the invention relates to a method for synthesizing a bi-redox-active bipolar compound according to the invention of formula Vlb: according to the following reaction scheme: step A) and in which - DCM is dichloromethyl, l <n<5,

[0071] R is selected from a hydrogen atom or an alkyl in (C1-C5).

[0072] According to an eleventh object, the invention relates to a method for synthesizing a bi-redox-active bipolar compound according to the invention of formula Vila:

[0073] according to the following reaction scheme: step A) and in which

[0074] DCM is dichloromethyl, n is between 1 and 5, R is selected from a hydrogen atom or an alkyl in (C1-C5).

[0075] According to a twelfth object, the invention relates to a method for synthesizing a bipolar redox-active compound according to the invention of formula Vllb: according to the following reaction scheme: step A) and in which

[0076] DCM is dichloromethyl, ACN is acetonitrile, n is between 1 and 5.

[0077] R is selected from a hydrogen atom or an alkyl in (C1-C5).

[0078] Brief descriptions of the drawings

[0079] [Fig 1]: Characterization by cyclic voltammetry of a bi-redox-active bipolar molecule according to the invention (compound no. 1).

[0080] [Fig 2]: Characterization by cyclic voltammetry of a bi-redox-active bipolar molecule of the invention (compound no. 2).

[0081] [Fig 3]: Characterization by cyclic voltammetry of a bi-redox-active bipolar molecule of the invention (compound no. 3).

[0082] [Fig 4]: Characterization by cyclic voltammetry of a bi-redox-active bipolar molecule of the invention (compound no. 4).

[0083] [Fig 5]: Example of the use of compound no. 4 in an electrochromic glazing type device: top panel, glazing in the discharged state; middle panel glazing in the charged state; bottom panel: arrangement of the layers composing the symmetrical electrochromic glazing incorporating compound no. 4.

[0084] [Fig 6]: illustration of the compound of formula VI belonging to sub-family 1 of compounds of formula Via according to the invention and mentioning the properties of the groups which constitute it.

[0085] Detailed description of the invention

[0086] A new family of multifunctional bi-redox-active bipolar molecules has been identified.

[0087] They may include electron donor and / or acceptor fragments in their structure.

[0088] They may also include proton donor and / or acceptor fragments, giving them acid-base properties.

[0089] They can also contain imidazolium fragments, giving them ionic liquid-like properties. Molecules in this family are therefore modular, depending on the groups they contain.

[0090] They can therefore include different chemical groups in order to modulate their solubility under different conditions and / or to produce ionic liquids.

[0091] Furthermore, depending on the groups used, the bi-redox organic molecules of the invention possess the different functionalities necessary for energy storage and electrochromic applications, and electrocatalytic applications.

[0092] These bipolar redox-active compounds are organic; they do not include rare materials or metals, or critical metals, or heavy metals.

[0093] They therefore represent a sustainable solution to be integrated into electrochemical energy storage devices such as systems containing liquid or solid electrolytes like organic batteries, supercapacitors, supercaberies (combining high energy density and high power density) and redox flow batteries.

[0094] Their synthesis is simple and requires only a small number of steps, and does not use rare materials or rare metals, or critical metals, or heavy metals.

[0095] The term "optional", referring to a chemical group of a bipolar bi-redox-active compound of the invention, is understood to mean that said compounds of the invention may or may not include this group, which, when absent, is not replaced by any other group.

[0096] The terms "(C1-C5) alkyl" or "C1-C5 alkyl" used in the present invention refer to a saturated, linear or branched hydrocarbon chain comprising from 1 to 5 carbon atoms, including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Preferably, the terms "(C1-C5) alkyl" or "C1-C5 alkyl" used in the present invention refer to a linear (i.e., unbranched) saturated hydrocarbon chain. The term "viologen," when referring to a chemical group of one of the compounds of the invention refers to a group of formula

[0097] The term "quinone," when referring to a chemical group of one of the compounds of the invention, refers to a group of formula

[0098] The term "anthraquinone," when referring to a chemical group of one of the compounds of the invention, refers to a group of formula

[0099] ACTIVE BI-REDOX COMPOUNDS OF THE INVENTION

[0100] Thus, a first object of the invention relates to the family of molecules of formula (I) as described above. All the compounds of the invention, such as those of the subfamilies listed below, are polar compounds which therefore have the advantage of being soluble in different polar media such as water and acetonitrile.

[0101] The range of compatible solvents is therefore particularly broad, and so are the potential applications, compared to other compounds in the art. For example, the compounds of the invention can be used in eutectic solvents, or even deep eutectic solvents, which are greener and of limited toxicity compared to the usual solvents in the field of electrochemistry, or even in liquid solutions advantageously of the "solvent in a salt" type, which are known to have better electrochemical stability and therefore allow implementation in wider potential ranges.

[0102] In a particular embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 1 of the family of compounds of the invention in which:

[0103] A is a group selected from the following groups: o an amino alkyl of formula in which R is selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5, et o un amino alkyl imidazolium de formule in which R is selected from a hydrogen atom or an alkyl group in (Ci-

[0104] C5), and l <n<5 ; ou un amino alkyl imidazolium de formule in which R is selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5 et l<m<5 ; B est un groupement de type : o anthraquinone, ou o quinone.

[0105] It doesn't exist.

[0106] In an even more particular embodiment of the compounds of the invention of subfamily 1, group B is anthraquinone.

[0107] In an even more particular embodiment of the compounds of the invention of subfamily 1, group B is quinone.

[0108] As illustrated in the experimental data relating to compound no. 1, the compounds in this group are compounds with electrochemical properties relevant for their use in energy storage devices as will be detailed below.

[0109] When A is an aminoalkyl group, the solubility of the compounds can be modulated by the acid-base conditions of the environment, giving them a wide range of applications. This property can also be used to modulate the interaction of these molecules with other electrode components in electrochemical applications. These molecules are also easily recycled and / or reused, since modulating their solubility allows for their straightforward recovery for later use. Therefore, these molecules are particularly valuable from a resource conservation perspective.

[0110] In another particular embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 2 of the family of compounds of the invention in which: A is an amino alkyl of formula in which R is selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5,

[0111] B is a group exhibiting a grouping of the type: o anthraquinone, or o quinone,

[0112] It is an aminoalkyl-TEMPO group of formula in which R is selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5.

[0113] Compounds in subfamily 2 therefore contain two TEMPO groups. These molecules allow for particularly rapid charge transfer, and are thus of particular interest for electrochemical applications.

[0114] As mentioned previously for sub-family 1, the presence of the aminoalkyl group can modulate the solubility of the compound by controlling the acid-base conditions of the environment, which gives these compounds a wide range of applications (particularly with regard to electrode components in electrochemical applications) and facilitates their recycling and / or reuse.

[0115] In a further particular embodiment, the bipolar bi-redox-active compound according to the invention is a compound of subfamily 2 in which:

[0116] A is an amino alkyl group of formula] ,

[0117] B has an anthraquinone-type group, and C is an aminoalkyl-TEMPO group of formula

[0118] R being selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5.

[0119] Among the molecules of subfamily 2, these molecules are particularly stable compared to members of the family for which B is a quinone.

[0120] As illustrated in the experimental data relating to compound no. 2, the compounds in this group are compounds with electrochemical properties relevant for their use in energy storage devices as will be detailed below.

[0121] In another, even more specific embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 2 in which:

[0122] A is an amino alkyl group with the formula ,

[0123] B presents a quinone-type grouping, and

[0124] It is an aminoalkyl-TEMPO group with the formula

[0125] R being selected from a hydrogen atom or an alkyl group in (C1-C5), and l <n<5.

[0126] Among the molecules of subfamily 2, these molecules are particularly soluble compared to members of the family for which B is an anthraquinone.

[0127] Bipolar bi-redox-active compounds. In another particular embodiment, the bipolar bi-redox-active compound according to the invention is a compound of subfamily 3 of the family of compounds of the invention in which:

[0128] A is a C1-C5 alkyl group,

[0129] B has a viologenic-type group of formula

[0130] , And

[0131] It is a group chosen from: o butane 1 sulfonate, and o butane 1 carboxylate.

[0132] The compounds in this subfamily are therefore zwitterions whose solubility can be modulated according to the ionic strength of the solvent, which is of interest for the recycling and / or reuse of these compounds, and diversifies the possibilities of interaction with the other components (and therefore the choice of these compounds) of the electrode in electrochemical applications.

[0133] Furthermore, zwitterionic properties allow for a further expansion of the range of choices of polar solvents compatible with these compounds.

[0134] In addition, these compounds have the advantage of being usable as both cathodic and anodic materials, which is of particular interest in terms of resource conservation and ease of recycling.

[0135] In a further particular embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 3 of the family of compounds of the invention in which:

[0136] A is a C1-C5 alkyl group,

[0137] B is a viologen-type group with the formula C is butane-1-sulfonate

[0138] In a further particular embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 3 of the family of compounds of the invention in which:

[0139] A is a C1-C5 alkyl group,

[0140] B is a viologenic-type group with the formula and

[0141] This is butane 1 carboxylate

[0142] As illustrated in the experimental data for compound #3, the compounds in this group possess electrochemical properties relevant for use in energy storage devices, as detailed below (Figure 3). Furthermore, these compounds are particularly well-suited to electrochromic applications, as illustrated in Figure 5, and also allow for the fabrication of symmetrical electrochromic devices, since the same compound can be used at both the cathode and anode of the electrochemical device.

[0143] In another particular embodiment, the bipolar redox-active compound according to the invention is a compound of subfamily 4 of the family of compounds of the invention in which:

[0144] A is a C1-C5 alkyl group,

[0145] B is a viologenic-type group with the formula

[0146] It is an alkenyl group with the formula in which the <m<5.

[0147] Bipolar redox-active compounds of subfamily 4, due to their vinyl chemical function, have the advantage of being polymerizable and able to be grafted onto surfaces of interest. Methods for grafting vinyl functions are well-established, such as surface atom transfer polymerization (SI-ATRP) (Zoppe et al., 2017); or the electrochemical reduction of vinyl compounds on a carbon electrode (Gabriel et al., 2010), which leads to the formation of a polymer layer that adheres strongly to the electrode surface.

[0148] As illustrated in the experimental data relating to compound no. 4, the compounds in this group constitute compounds with relevant electrochemical properties (figure 4) for their use in energy storage devices as will be detailed below.

[0149] Due to the presence of the viologenic group, compounds in this subfamily are also particularly suited to electrochromic applications.

[0150] When a quaternary amine is present in any of the bipolar redox-active compounds according to the invention, a counter anion is associated with it. Most often, the counter anion(s) is / are introduced during the synthesis of the bipolar redox-active compound of the invention, along with the synthetic intermediates to which they are associated. Metathesis methods are well known in the art (Bodin et al., 2023).

[0151] In a particular embodiment, the associated counter anion is selected from Br, Cl', their mixtures. The counter-amun is of particular interest in electrochemical applications because it allows applications associated with ionic liquids; it also allows increasing the charge density of electrochemical systems compared to systems including the other aforementioned anions.

[0152] A counter anion synthesis process may include the following steps:

[0153] (i) the addition by drop-by-drop, over a period of between 120 and 180 minutes, of a molar equivalent of chlorosulfonic acid into a suspension of 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl in anhydrous diethyl ether maintained between 0°C and 5°C,

[0154] (ii) stirring the mixture at room temperature for at least 24 hours, preferably at least 40 hours,

[0155] (iii) cooling the reaction mixture to between 0°C and 5°C, then adding 2 molar equivalents of phosphorus trichloride and stirring the mixture for at least 1 hour, preferably at least 2 hours, between 0°C and 5°C, followed by stirring at room temperature for at least 12 hours, preferably at least 24 hours at room temperature,

[0156] (iv) evaporation of the solvent under reduced solvent pressure, the residual solid being (2,2,6,6-tetramethylpiperidine-N-oxyl)chlorosulfate,

[0157] (v) (2,2,6,6-tetramethylpiperidine-N-oxyl)chlorosulfate is placed in acetonitrile, then 1 molar equivalent of trifluoromethanesulfonamide and 1 molar equivalent of the carbonate metal salts are added, then the mixture is maintained at 70°C under stirring for at least 24 hours,

[0158] (vi) Acetonitrile is evaporated, the crude product is dissolved in absolute ethanol, the resulting mixture is filtered to remove the carbonate,

[0159] (vii) the liquid phase is evaporated under reduced pressure for the counter anion of formula: which is associated with a metallic cation.

[0160] The bipolar active bi-redox compounds according to the invention are, therefore, due to their properties as illustrated in the experimental section, particularly suited for use as electronic conductors in electrical conductors, or as electronic relays for electron transfer in redox systems such as energy storage systems (e.g., a supercapacitor, a solid-state battery, a redox flow battery, a symmetrical battery), and catalytic systems using either chemical or enzymatic catalysts (in bioelectrochemical systems). This use constitutes a third object of the present invention.

[0161] A third object of the invention is the use of at least one bi-redox-active bipolar compound according to the invention in an electrochemical system.

[0162] The bipolar redox-active compounds according to the invention can be used to create electrochemical energy storage systems (supercapacitors, solid-state batteries, redox flow batteries), electrochromic systems, and electrochromic batteries using the symmetrical battery concept. The bipolar redox-active compounds according to the invention are suitable for charge transfer in conducting systems, as demonstrated by experimental data: these compounds enable, in particular, the storage and release of energy (Table 2). They are therefore particularly well-suited for implementing electrochemical reactions that take place at the interface of two conducting systems (electronic: electrodes; ionic: solutions) associated with charge transfer involving one or more electrons.

[0163] From the above, it appears that the compounds of the invention, by virtue of their modularity, can either be immobilized, for example by printing methods (additive manufacturing) at the anode and / or at the cathode, or present in solution according to the specificities of the electrochemical system.

[0164] In one particular embodiment, in an electrochemical system according to the invention comprising at least one bipolar redox-active compound according to the invention, said at least one bipolar redox-active compound is immobilized, for example, by printing methods (additive manufacturing) at the anode and / or the cathode. In another particular embodiment, in an electrochemical system, said at least one bipolar redox-active compound is immobilized, for example, by printing methods (additive manufacturing) at both the anode and the cathode. Immobilization, as defined in the invention, means any process resulting in the permanent association of the compounds of the invention with the cathode and / or the anode.

[0165] Another method of immobilization is the covalent bonding of the compounds to the cathode and / or the anode, for example by means of a grafting as previously mentioned for the compounds of the invention in subfamily 4, using at least one compound of the invention having a vinyl group. The covalent bonding of the compounds to the electrodes is particularly robust.

[0166] Another alternative is to incorporate the compounds of the invention into the material constituting the anode and / or cathode or surface. Obviously, the charge per unit mass in this embodiment will be lower, but the materials incorporating the compounds according to the invention retain their advantages.

[0167] In another particular embodiment, the at least one bipolar redox-active compound immobilized at the anode and cathode is the same compound. In this embodiment, compounds of the invention particularly suitable for this purpose are those of subfamily 3. This is of particular advantage in terms of resource conservation and recycling.

[0168] In another particular embodiment, the at least one bipolar bi-redox-active compound immobilized at the anode is different from that used at the cathode.

[0169] In one embodiment, in an electrochemical system according to the invention, comprising at least one bipolar bi-redox-active compound according to the invention, said at least one bipolar bi-redox-active compound is present in solution.

[0170] The compounds of the invention are therefore suitable for a wide variety of electrolytes. They are particularly well-suited to semi-solid electrolytes. Bio-based semi-solid electrolytes are biopolymers, such as polysaccharides (e.g., cellulose, α-iginate, chitin / chitosan) and protein-based polymers (e.g., silk, gelatin), which are attractive building blocks for durable, bioavailable, and inexpensive electronic devices that are at least partially biodegradable and suitable for the compounds of the invention. This is illustrated by the electrochemical glass described in the experimental section below. Suitable semi-solid electrolytes are described, for example, by Xu et al. (2022) and Zhou et al. (2024).

[0171] ELECTROCHEMICAL ENERGY STORAGE DEVICE

[0172] A fourth object of the invention lies more particularly in an electrochemical energy storage device comprising at least one bipolar bi-redox-active compound according to the invention which is used therein for its electrochemical properties.

[0173] The compounds according to the invention exhibit improved solubility and stability. They can also be grafted onto solid supports. Furthermore, they exhibit good solubility in polar solvents. This solubility can also be modulated, particularly for compounds in subfamilies 1, 2, and 3, depending on the physicochemical conditions under which they are used (for example, pH, ionic strength). Combined with their electrochemical properties, this opens up a wide range of applications in the field of energy storage, and especially in energy storage systems such as flexible, solid-state embedded systems, to meet the emerging needs of new sensor technologies and connected devices.

[0174] The bipolar redox-active compounds according to the invention are therefore particularly suitable for energy storage devices such as, but limited to: redox flow batteries (RFBs), micro batteries, supercapacitors, supercabatteries (system combining the properties of supercapacitors and those of batteries), electrochromic systems, electrochromic batteries, and solid-state energy storage systems.

[0175] In a particular embodiment, the invention relates to an electrochromic device of the electrochromic battery type comprising a compound of subfamily 2 or 3, which produces a color change during the charge / discharge process.

[0176] Such compounds find their application in particular in electrochromic glazing.

[0177] The performance of the compounds according to the invention in such electrochromic systems is illustrated in Figure 5.

[0178] METHOD FOR SYNTHESIZING COMPOUNDS

[0179] A fifth object of the invention relates to the processes for synthesizing the compounds described above in the brief summary of the invention:

[0180] EXAMPLES

[0181] Abbreviations used:

[0182] DCM: dichloromethane

[0183] DMF: dimethylformamide

[0184] ACN: acetonitrile 4-OH-Tempo: 4-Hydroxy-2,2,6,6-tetramethyl-l-piperidin-l-yloxy, free radical

[0185] SCE: saturated calomel electrode

[0186] RT: ambient temperature

[0187] THF: tetrahydrofuran

[0188] 1. Synthesis of the compounds of the invention. General synthesis methods.

[0189] • Compounds of subfamily 1 (formula (Via) or (Vlb))

[0190] Method for synthesizing a compound with formula (Via): 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0-5°C for 4 hours, then left at room temperature for 18 hours.

[0191] The organic phase is extracted, washed, and the solvent is evaporated. Imidazole (Sigma-Aldrich, France) in tetrahydrofuran is then added. Next, NaH is introduced into the reaction. The mixture is stirred at 50°C for 18 hours. After the reaction, the solvent is evaporated to obtain a crude product, which is then dissolved in DCM. The organic phase is then washed with water and dried with anhydrous MgSC. The solvent is evaporated using a rotary evaporator to obtain a viscous, reddish-brown product. (Step B)

[0192] A 2-aminoalkyl quinone (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0–5°C for 4 hours and then left at room temperature for 18 hours.

[0193] The organic phase is extracted, washed, and the solvent is evaporated. (Step C) The product obtained in step B is dissolved in DCM. The DCM containing the compound obtained in step A is added to the reaction. The reaction is maintained under stirring at 50°C for 2 days. After the reaction, the solvent is evaporated to obtain the crude product. This is then washed with diethyl ether. The final compound is obtained as a brown solid.

[0194] Synthesis process for a compound with formula (Vlb): according to the following reaction scheme: step A)

[0195] 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine (Sigma-

[0196] Aldrich, France) is added to the flask under argon, and the mixture is left under agitation at between 0 and 5°C for 4 hours and then at room temperature for 18 hours.

[0197] The organic phase is extracted, washed, and the solvent is evaporated. (Step B)

[0198]

[0199] (VW

[0200] The product obtained in step A is dissolved in DCM in a round-bottom flask, and then aminoanthraquinone (Sigma-Aldrich, France) dissolved in acetonitrile is added. The reaction is carried out under stirring at 50°C for two days. After the reaction, the solvent is evaporated using a rotary evaporator. The crude product is rinsed with diethyl ether. The final compound is obtained as a brown solid.

[0201] The same procedures apply, mutatis mutandis, to the case where group B is a quinone (compounds of formulas Vila and VI I b) • Compounds of subfamily 2

[0202] The compounds of subfamily 2 (of formula (Ilia) or ( 111 b))

[0203] can be synthesized according to the following synthesis route: - step A)

[0204] 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0-5°C for 4 hours and then left at room temperature for 18 hours.

[0205] The organic phase is extracted, washed, and the solvent is evaporated.

[0206] -step B) with 40 <X<60, et R sélectionné parmi est sélectionné parmi un atome d'hydrogène ou un alkyle en (C1-C5) Le produit obtenu à l'étape A est dissout dans 30mL d'ACN dans un ballon. Un 2,6 diaminoalkyl anthraquinone ou de 2,5-diaminoalkyl-l,4-benzoquinone (Sigma-Aldrich, France) est dissout dans de l'ACN et ajouté au mélange. La réaction est laissée sous agitation à 70°C. Après la réaction le solvant est évaporé, le produit brut est rincé.

[0207] • Composed of subfamily 3

[0208] Synthesis process for a compound with formula (Iva):

[0209] 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The (C1-C5) acyl chloride solution (Sigma-Aldrich) is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0–5°C for 4 hours and then left at room temperature for 18 hours.

[0210] The organic phase is extracted, washed, and the solvent is evaporated. (Step B) 4,4'-Bipyridyl (Sigma-Aldrich, France) is dissolved in distilled ACN, then, under argon, 1,3-propane sulfone (Sigma-Aldrich, France) dissolved in distilled ACN is added dropwise. The mixture is kept under stirring at 80°C, the product (white powder) is filtered and washed. (Step C)

[0211] The compound obtained in step A is dissolved in distilled N,N-dimethylformamide in a reaction flask. A solution of the compound obtained in step B dissolved in N,N-dimethylformamide is then added to the flask, and the mixture is stirred at 70°C. After the reaction, the solvent is evaporated. The crude product is washed. In the case illustrated here, the chloride anions are provided by the reaction intermediates. They can be readily exchanged by metathesis according to methods commonly used in the art. Process for the synthesis of a compound of formula (IVb): according to the following reaction scheme: step A)

[0212] O

[0213] 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0-5°C for 4 hours and then left at room temperature for 18 hours.

[0214] The organic phase is extracted, washed, and the solvent is evaporated. (Step B)

[0215] In a flask containing one equivalent of 4,4'-Bipyridyl (Sigma-Aldrich, France) in 10 mL of acetonitrile solvent, one equivalent of 4-Bromobutyric acid (Sigma-Aldrich, France) was added while stirring. The solution was refluxed for 18 hours at 80 °C. After the reaction, a yellow solid formed, which was then filtered and washed with acetonitrile. (Step C)

[0216] The compound obtained in step A ) is dissolved in distilled N,N-dimethylformamide in a reaction flask. A solution of the compound obtained in step B dissolved in N,N-dimethylformamide is then added to the flask, and the mixture is stirred at 70°C. After the reaction, the solvent is evaporated. The crude product is washed. In the case illustrated here, the chloride anions are provided by the reaction intermediates. They can easily be exchanged by metathesis according to methods commonly used in the art.

[0217] • Composed of subfamily 4

[0218] Synthesis process for a compound of formula (V):

[0219]

[0220] 4-OH-Tempo (Sigma-Aldrich, France) is dissolved in distilled DCM. The acyl chloride (C1-C5) solution is added dropwise under argon. Pyridine is added to the flask under argon, and the mixture is stirred at 0-5°C for 4 hours, then left at room temperature for 18 hours. The organic phase is extracted, washed, and the solvent is evaporated. The crude product is washed. (Step B)

[0221] DCM

[0222] At 50°C, 18-24 h, 4,4'-bipyridine I is dissolved in DCM under vigorous stirring. Alkyl bromide (Cl-C4) dissolved in DCM is added dropwise to the mixture, then held at 50°C under stirring. After the reaction, the solution is filtered. The solid is washed. The organic solvent is evaporated under reduced pressure, resulting in a solid as well. The crude product is recrystallized in a dichloromethane:hexane mixture (1:20). The product is dried under vacuum. (Step C)

[0223] The compounds from the previous steps are mixed in a flask with distilled ACN. The reaction is maintained under stirring at 50°C. After the reaction, the crude product is recrystallized. In the case illustrated here, the chloride and bromide anions are introduced by the reaction intermediates. They can be readily exchanged by metathesis according to methods commonly used in the art.

[0224] 1.2 Examples of synthesis • Compound no. 1

[0225] Compound No. 1 Step A: 4-OH-Tempo (25 mmol) is dissolved in 20 mL of distilled DCM. The solution is cooled to 0°C. 27.7 mmol (in 20 mL of DCM) of chloroacetyl chloride is then added dropwise under argon. 27.5 mmol of pyridine is added to the flask under argon, and the mixture is left to stand under stirring at 0–5°C for 4 hours and then at room temperature for 18 hours.

[0226] After the reaction, the organic phase is extracted with 20 mL of 3 M HCl, then washed with 20 mL of a saturated NaCl solution. The remaining DCM in the filtrate is dried with anhydrous MGSO4, and the solvent is then evaporated using a rotary evaporator. A reddish-brown liquid product is obtained (90% yield).

[0227] Step B: The product obtained 8 mmol of 2-aminoanthraquinone is dissolved in 30 mL of ACN in a round-bottom flask. 10 mmol of 2-aminoanthraquinone dissolved in ACN is then added. The reaction is left to proceed with stirring at 70°C for 2 days. After the reaction, the solvent is evaporated using a rotary evaporator. The crude product is rinsed four times with 30 mL of ACN, then four times with 30 mL of diethyl ether; compound no. 1 is obtained as a brown solid (yield 74%).

[0228] 1H NMR (DMSO-d6) 6: 8.1 (2H), 7.8 (2H), 7.3 (1H), 6.95 (1H), 6.7 (2H), 5.2 (1H), 4.4 (6H), 1.5 (12H)

[0229] 13C NMR (DMSO- d6) 6: 184 (IC), 180 (IC), 167 (IC), 155, (IC), 135.4 (IC), 134.8 (IC), 134.2, (IC), 133.9, (IC), 133.5 (IC), 130.1 (IC), 130 (IC), 126.9 (IC), 126.8 (IC), 121.5 (IC), 118.5 (IC), 110.14 (IC), 56.93 (IC), 29.6 (4C), 25.56 (IC).

[0230] Compound No. 2

[0231] Compound 2

[0232] Step A: 4-OH-Tempo (25 mmol) is dissolved in 20 mL of distilled DCM. The solution is cooled to 0°C. 27.7 mmol (in 20 mL of DCM) of chloroacetyl chloride is then added dropwise under argon. 27.5 mmol of pyridine is added to the flask under argon, and the mixture is stirred at 0–5°C for 4 hours and then left at room temperature for 18 hours.

[0233] After the reaction, the organic phase is extracted with 20 mL of 3 M HCl, then washed with 20 mL of a saturated NaCl solution. The remaining DCM in the filtrate is dried with anhydrous MGS04, and the solvent is then evaporated with a rotary evaporator. A reddish-brown liquid product is obtained (90% yield).

[0234] Step B: The product obtained A 2,6-diaminoalkyl anthraquinone is dissolved in 50 mL of an ACN / DCM (50 / 50 v / v) mixture and added dropwise to 50 mL of a 50 mL ACN / DCM (50 / 50 v / v) mixture. The reaction mixture is stirred at 50°C for 24 hours. After the reaction, the solvent is evaporated to obtain a brown solid. A reddish-brown solid corresponding to compound 3 is obtained following purification by silica gel chromatography to ethyl acetate (56% yield). X H NMR (DMSO-d6) 6: 1.44 (24H), 1.0 (4H), 4.42 (8H), 5.2 (2H), 6.5 (2H), 6.8 (2H), 7.8 (2H), 7.2 (2H).

[0235] 13 C NMR (DMSO- d6): 6 25 (8C), 30 (2C), 56.9 (4C), 67 (4C), 110 (2C), 117 (2C), 121 (2C), 130 (2C), 133 (2C), 136 (2C), 155 (2C), 167 (2C), 181 (2C).

[0236] • Compound No. 3

[0237] Compound No. 3

[0238] 4-OH-Tempo (25 mmol) is dissolved in 20 mL of distilled DCM. The solution is cooled to 0°C. 27.7 mmol (in 20 mL of DCM) of chloroacetyl chloride is then added dropwise under argon. 27.5 mmol of pyridine is added to the flask under argon, and the mixture is left to stand at room temperature for 24 hours with stirring.

[0239] After the reaction, the organic phase is extracted with 20 mL of 3 M HCl, then washed with

[0240] 20 mL of a saturated NaCl solution. The remaining DCM in the filtrate is dried with

[0241] Anhydrous MGSO4 is used, and the solvent is then evaporated with a rotary evaporator. A reddish-brown liquid product is obtained (90% yield). 4,4'-Bipyridyl (16 mmol, 2.5 g, leq) is dissolved in 15 mL of distilled ACN, then 1,3-Propane sultone (16 mmol, 1.96 g, leq) in 15 mL of distilled ACN is added dropwise under argon. The mixture is kept under stirring at 80°C for 4 hours. The product (white powder) is filtered and washed four times successively with 50 mL (99% yield). Step C: The compound obtained (3.75 mmol) is dissolved in 20 mL of distilled DMF in a reaction flask. A solution of the compound obtained in step B in 10 mL of DMF (3.13 mmol) is then added to the flask, and the mixture is stirred at 70°C for 2 days. After the reaction, the solvent is evaporated using a rotary evaporator. The crude product is washed four times successively: four times with 20 mL of toluene, and four times with 30 mL of acetone. An orange-brown product is obtained (yield 83%).

[0242] X H NMR (D2O) 6: 8.9 (2H), 8.7 (2H), 8.4 (2H), 7.9 (2H), 5.3 (1H), 4.7 (4H), 4.3 (1H), 2.6 (4H), 1-

[0243] 1.4 (2 PM)

[0244] 3 C NMR (D2O) 6: 25.1 (4C), 31.3 (IC), 34.4 (IC), 36.8 (2C), 47.0 (2C), 59 (IC), 123 (1C), 126 (IC),

[0245] 145 (IC), 148 (4C), 153 (4C), 164 (IC)

[0246] • Compound No. 4

[0247] Compound No. 4

[0248] Step A: 4-OH-Tempo (25 mmol) is dissolved in 20 mL of distilled DCM. The solution is cooled to 0°C. 27.7 mmol of chloroacetyl chloride (in 20 mL of DCM) is then added dropwise under argon. 27.5 mmol of pyridine is added to the flask under argon, and the mixture is left to stand at room temperature for 24 hours with stirring.

[0249] After the reaction, the organic phase is extracted with 20 mL of 3 M HCl, then washed with 20 mL of a saturated NaCl solution. The remaining DCM in the test filtrate is dried with anhydrous MGSO4, and the solvent is then evaporated with a rotary evaporator. A reddish-brown liquid product is obtained (90% yield). Step B: In a three-necked flask, 4,4'-bipyridyl (3.2 g, 20 mmol) is dissolved in 100 mL of DCM with vigorous stirring. A solution of allyl bromide (2 mL, 24 mmol) in a final volume of 40 mL of DCM is added dropwise to the mixture, then held at 50°C overnight with stirring. The solution is then filtered: a yellow solid and a yellow solution are obtained. The solid is washed with DCM, resulting in 1,l'-dia I lyl-[4,4'-bipyridine]-1,l'-diium. The organic solvent is evaporated under reduced pressure, resulting in a yellow solid.The crude product was recrystallized in a dichloromethane:hexane mixture (1:20), resulting in a yellow powder. The purified product was then dried under vacuum.

[0250] (Yield: 70%, 1.94 g)

[0251] The compound obtained in step A (2 mmol) is dissolved in 20 mL of distilled ACN in a round-bottom flask. 10 mL of an ACN solution containing 2 mmol of the compound obtained in step B is added to the flask. The reaction is maintained under stirring at 50°C for 2 days. After the reaction, the crude product is recrystallized twice in diethyl ether, resulting in a white solid (50% yield).

[0252] 1H NMR (DMSO- d6) 6: 9.2 (2H), 8.88 (2H), 8.67 (2H), 8.0 (2H), 6.2 (1H), 5.87 (1H), 5.76 (1H),

[0253] 5.5 (2H), 5.3 (2H), 4.4 (4H), 1.24(12H).

[0254] 3C NMR (DMSO-d6): 628.1-28.3 (4C), 46.3 (2C), 49.0 (IC), 51.7 (IC), 64.1 (2C), 68.1 (IC), 117.7 (IC), 121.0-121.1 (4C), 129.3 (4C), 132.8 (IC), 166.8 (IC).

[0255] 2. Electrochemical performance

[0256] Cyclic voltammetry is an electrochemical technique used to study the redox properties of electroactive chemical compounds at the electrode interface in a solution.

[0257] This technique is based on scanning a linear, contrasting potential at a given scan rate for a stationary or rotating electrode. The signal obtained with this technique is the faradaic current, that is, the current due to the redox reaction of electroactive species in solution or immobilized on the electrode surface. A three-electrode system is required to use this technique: a reference electrode, a working electrode, and an auxiliary electrode.

[0258] A supporting electrolyte is always added to the solution to maintain sufficient conductivity. The potential is measured with the working electrode and the reference electrode, while the current is measured with the working electrode and the auxiliary electrode.

[0259] The voltage usable for battery-type electrochemical energy storage is the formal separation of potential peaks (AE) between the electron donor and acceptor AE (in volts), determined and reported in Table 2 below and the associated figures. [Table 2]

[0260] + ImM in an aqueous solution of O.IM KCl; 100 mV / s

[0261] ¥ 4OH Tempo § anthraquinone, quinone or viologen group

[0262] Such electroactive compounds are therefore particularly suited for use in electrochemical energy storage devices; these devices are based on the bipolar bi-redox-active compounds of the invention which are purely organic.

[0263] Due to their bipolar properties, these bi-redox-active bipolar molecules can be used as cathode and anode within the same electrochemical system based on the concept of a symmetric battery, an example of which is illustrated below in the context of an application in electrochromic glazing.

[0264] It should be noted that the AE for the compounds of the invention is particularly high compared to what is observed for each of the acceptors or donors considered in isolation (generally on the order of 1-1.2 V).

[0265] 3. Electrochromic Applications

[0266] An electrochromic glazing with a symmetrical structure, comprising layers 1-7 as shown in Figure 5, is produced. These symmetrical glazings are particularly advantageous from the point of view of the simplicity of their synthesis process and the cost reduction that can be expected due to the use of the same compounds at the anode and cathode.

[0267] Layers 1 and 7 glass support

[0268] Layers 2 and 6: transparent electrode made of tin-doped indium oxide.

[0269] Layers 3 and 5, compound 4 is incorporated into an ionogel comprising an aqueous solvent to obtain the following composition (in mass percentage):

[0270] 2% carboxymethyl cellulose,

[0271] 2% compound 4,

[0272] IM ionic liquid: l-ethyl-2,3-dimethylimidazolium ethyl sulfate,

[0273] 1% tannic acid,

[0274] 1% gelatin.

[0275] Layer 4 is composed of an ionogel such as that of layers 3 and 5, without the electrochromic biredox compound of the invention. The ionogel used in layers 3, 4, and 5 is a biogel comprising bio-based elements such as gelatin, carboxymethyl cellulose, and tannic acid.

[0276] The top panel of Figure 5 shows that in the discharged state the electrochromic glazing is transparent, while in the charged state (middle panel) the electrochromic glazing is tinted.

[0277] Such glazing comprising a bi-redox compound according to the invention therefore combines charge storage properties and electrochromic properties, making it possible to create devices for monitoring the state of charge of the organic battery.

[0278] REFERENCES

[0279] Justin O. Zoppe, Nariye Cavusoglu Ataman, Piotr Mocny, Jian Wang, John Moraes and Harm- Anton Klok, Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineeringwith Polymer Brushes. Chem. Rev. 117 (2017) 1105-1318.

[0280] Sabine Gabriel, Robert Jérôme, Christine Jérôme. Cathodic electrografting of acrylics: From fundamentals to functional coatings. Progress in Polymer Science 35 (2010) 113-140],

[0281] C. Bodin, B. Gelinas, J. Deng, Kulika Pithaksinsakul, Y. Zhu, D. Rochefort, O. Fontaine. Describing the unsuspected advantage of redox ionic liquids applied to electrochemical energy storage. Current Opinion in Colloid & Interface Science 2023, 64, 101677.

[0282] Xu, Ting & Liu, Kun & Sheng, Nan & Zhang, Minghao & Liu, Wei & Huayu, Liu & Dai, Lin & Zhang, Xinyu & Chuanling, Si & Du, Haishun & Zhang, Kai. (2022). Biopolymer-based hydrogel electrolytes for advanced energy storage / conversion devices: Properties, applications, and perspectives. Energy Storage Materials, 2022, 48 244-262.

[0283] Zhou X, Zhou Y, Yu L, Qi L, Oh KS, Hu P, Lee SY, Chen C. Gel polymer electrolytes for rechargeable batteries toward wide-temperature applications. Chem Soc Rev. 2024 Apr 18.

Claims

DEMANDS 1. A bipolar bi-redox-active compound of general formula I in which: A is selected from: o an aminoalkyl of formula , where R is selected from a hydrogen atom or an alkyl group in (C1-C5), and n is between 1 and 5, o an amino alkyl imidazolium of formula hydrogen atom or an alkyl in (C1-C5), and n and m are independently between 1 and 5, and o an alkyl in (C1-C5) B is an electron acceptor group, selected from a viologen, anthraquinone, or quinone type group, This is an optional group selected from: o a polymerizable function which is a C3-C6 α-olefin, with the formula: o a selected task force from among or an electron donor group selected from the group of formula II in which R is selected from a hydrogen atom or a C1-C5 alkyl and n is between 1 and 5; when group A is a (C1-C5) alkyl it is bonded to a viologen-type group B and group B is itself bonded to a C group.

2. Bipolar bi-redox-active compound according to claim 1, wherein the electron acceptor group B has a viologen-type group.

3. Bipolar bi-redox-active compound according to claim 2, wherein C is selected from: the polymerizable function which is a C3-C6 α-olefin, of formula between 1 and 4, or a task force selected from 4. Bipolar bi-redox-active compound according to claim 1, wherein the electron acceptor group B has a quinone-type group anthraquinone-type group 5. Bipolar bi-redox-active compound according to claim 4, wherein group B has a quinone or anthraquinone type group, group A is an aminoalkyl or amino alkyl imidiazolium, and a group C is present.

6. Bipolar bi-redox-active compound according to claim 4 or 5, wherein C is the electron-donating group of formula II in which R is selected from a hydrogen atom or a C1-C5 alkyl and n is between 1 and 5.

7. Bipolar bi-redox-active compound according to claim 1, said bipolar bi-redox-active compound having the formula Ilia or Hlb: with R selected from a hydrogen atom or an alkyl in (C1-C5), and n and m are independently between 1 and 5.

8. Bipolar bi-redox-active compound according to claim 1, said bipolar bi-redox-active compound being of formula IVa or IVb: with n between 1 and 5.

9. Bipolar bi-redox-active compound according to claim 1, said bipolar bi-redox-active compound having formula V: with m between 1 and 4 and n between 1 and 5.

10. Bipolar bi-redox-active compound according to claim 1, wherein said bipolar bi-redox-active compound is of formula Via or Vlb: (Vlb), with R selected from a hydrogen atom or an alkyl in (C1-C5), and n and m are independently between 1 and 5.

11. Bipolar bi-redox-active compound according to claim 1, said bipolar bi-redox-active compound being formula Vila or VI I b: (Vila) (Vllb), with R selected from a hydrogen atom or an alkyl in (C1-C5), and n and m are independently between 1 and 5.

12. Bipolar bi-redox-active compound according to claim 1, said bipolar bi-redox-active compound being selected from the following compounds:

13. Bipolar bi-redox-active compound according to any one of claims 1 to 12, wherein when a quaternary amine is present, its counter anion is selected from , or mixtures thereof.

14. Bipolar bi-redox-active compound according to any one of claims 1 to 12, wherein, when charged, a counter-anion is selected from: Br-, Cl-, I-, , or mixtures thereof.

15. Bipolar bi-redox-active compound according to any one of claims 1 to 14, miscible in a polar solvent.

16. Use of a bipolar redox-active compound according to any one of the claims 1 to 15, like: - ionic liquid, and / or - electronic driver, and / or - electronic relay, for the transfer of electrons in redox systems such as energy storage systems, for example a supercapacitor, a solid battery, a redox flow battery, a symmetric battery, and catalytic systems.

17. Electrochemical system comprising at least one bipolar bi-redox-active compound according to any one of claims 1 to 15.

18. Electrochemical system according to claim 17, wherein said at least one bi-redox-active bipolar compound is immobilized at the cathode and / or immobilized at the anode, and / or is in solution.

19. Energy storage device such as a supercapacitor, a solid-state battery, a redox flow battery, a symmetric battery, comprising the electrochemical system according to any one of claims 17 or 18.

20. Electrochromic device such as an electrochromic battery, comprising an electrochemical system according to any one of claims 17 or 18, group B of the bipolar bi-redox compound having a viologen-type group.

21. Electro-catalytic device, comprising an electrochemical system according to any one of claims 17 or 18.

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