Electrochemical compounds for low current electrochromic devices.

Abstract

Anodic redox species comprising phenazine compounds substituted with at least one sterically hindered group and electrochromic devices using these chemical compounds are disclosed.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 311,694, filed February 18, 2022, which is hereby incorporated by reference in its entirety for all purposes.

[0002] The present technology relates generally to electrochromic devices. More specifically, it relates to redox compounds suitable for use in electrochromic devices that have persistent color memory and can provide electrical current during clearing for a significant period of time after charging. [Background technology]

[0003] Electrochromic devices have been well known for many years. When a sufficient electrical potential is applied to a pair of electrodes, an electrochromic medium placed between the electrodes can be activated and its color and / or light transmittance can be changed. Taking advantage of this, devices such as dimmable mirrors and windows are becoming increasingly popular in industry, for example in the automotive and aviation industries.

[0004] The present disclosure is directed to phenazine electrochromic materials having improved weather stability properties for use in electrochromic devices, particularly as anodic redox species attached or confined to polymer matrix films. Summary of the Invention

[0005] In one aspect, there is provided a compound represented by: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9are each independently H, F, Cl, Br, I, CF3, CN, OR 11 , S.R. 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups may be joined to form a monocyclic, polycyclic, or heterocyclic group; Each R 11 are independently H or alkyl; R 5 and R 10 is independent, (i) -L1-A-L2-OR 14 is represented by Each L1 is independently a C1-C8 alkylene group; Each L2 is independently a C1-C8 alkylene group; Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is alkyl or alkylhydroxy, or (ii) -L3-OR 16 is represented by Each L3 is independently a C1-C8 alkylene group; Each R 16 is H or alkyl, R 2 , R 3 , R 7 , and R 8 At least one of the groups is a sterically hindering group.

[0006] In some embodiments, the steric hindering groups are selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

[0007] In some embodiments, R1 , R 3 , R 4 , R 6 , R 8 , and R 9 are each independently H. In some embodiments, R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 are each independently H.

[0008] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of R is independently C2-C8 alkyl. 2 , R 3 , R 7 , and R 8 At least one of R is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 2 , R 3 , R 7 , and R 8 At least one of is independently isopropyl, neopentyl, or tertiary butyl.

[0009] In some embodiments, R 2 and R 7 , or R 2 and R 8 are each independently C2-C8 alkyl. 2 and R 7 , or R 2 and R 8 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 2 and R 7 , or R 2 and R8 is each independently isopropyl, neopentyl, or tertiary butyl.

[0010] In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently C2-C8 alkyl. 3 and R 8 , or R 3 and R 7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 3 and R 8 , or R 3 and R 7 is each independently isopropyl, neopentyl, or tertiary butyl.

[0011] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of is independently aryl. 2 , R 3 , R 7 , and R 8 At least one of is independently phenyl.

[0012] In some embodiments, R 2 and R 7 , or R 2 and R 8 Each is independently aryl. In some embodiments, R 2 and R 7 are each independently phenyl.

[0013] In some embodiments, R 3 and R 8 , or R 3 and R 7Each is independently aryl. In some embodiments, R 3 and R 8 , or R 3 and R 7 Each is independently phenyl.

[0014] In some embodiments, R 5 and R 10 At least one of the -L1-A-L2-OR 14 is represented by each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0015] In some embodiments, each L1 is independently a C2 or C4 alkylene group; each L2 is independently a C3 alkylene group; Each R 14 is H, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is C1 alkyl or C2 alkyl hydroxyl.

[0016] In some embodiments, R 5 and R 10 At least one of is independently represented by: [ka] n is 1, 2, 3, 4, 5, 6, 7, or 8; x is 1, 2, 3, 4, 5, 6, 7, or 8; Each R 15 is independently C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0017] In some embodiments, n is 2 or 4, x is 3, and each R 15 is independently C1 alkyl or C2 alkyl hydroxyl.

[0018] In some embodiments, R 5 and R 10 At least one of the -L3-OR 16 is represented by each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 16 is H or alkyl.

[0019] In some embodiments, each L3 is independently a C4 or C6 alkylene group, and each R 16 is H.

[0020] In some embodiments, R 5 and R 10 At least one of is independently represented by: [ka] y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0021] In some embodiments, y is 3 or 6.

[0022] In some embodiments, the compound is F - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6- , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , Al(OC(CF3)3)4 - , BAr4 - or a mixture of anions thereof, where Ar is an aryl group or a fluorinated aryl group. In some embodiments, the anion is PF6 - and SO3CF3 - is selected from.

[0023] In some embodiments, the compound is selected from: [ka] [ka] [ka] [ka] [ka]

[0024] In another aspect, A cathode material; an anode material; the cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, the first polymer matrix being configured to prevent or minimize substantial diffusion of the cathode material; An energy storage device is provided in which an anode material comprises any one or more of the phenazine compounds described herein covalently bonded to or confined within a second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the anode material.

[0025] In another aspect, a first cell including an anode material; a second cell including a cathode material; a porous separator separating the first cell from the second cell; the anode material comprises any one or more of any one of the phenazine compounds described herein; An energy storage device is provided in which the cathode material comprises a viologen.

[0026] In some embodiments, the energy storage device further comprises an electrolyte comprising a solvent and a metal salt or an ammonium salt. In some embodiments, the separator comprises an ion exchange membrane or a size exclusion membrane. In some embodiments, the energy storage device is a battery. [Brief description of the drawings]

[0027] [Figure 1] FIG. 1 shows the UV cycling durability (3 hr on / 1 hr off) of Device A and Device B described in the Examples. [Diagram 2] FIG. 2 shows the 85° C. cycling durability (3 hr on / 1 hr off) of Device A and Device B described in the Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] Various embodiments are described below. It should be noted that the specific embodiments are not intended as exhaustive descriptions or as limitations to the broader aspects described herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and may be practiced in any other embodiment.

[0029] As used herein, "about" will be understood by those of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are uses of the term that are unclear to those of ordinary skill in the art, taking into account the context in which it is used, "about" will mean up to plus or minus 10% of the particular period.

[0030] The use of the terms "a," "an," "the," and similar referents in the context of describing elements (particularly in the context of the claims below) are to be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each individual value within the range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually set forth herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. All examples provided herein, or the use of illustrative phrases (e.g., "such as"), are intended merely to better illustrate embodiments and do not limit the scope of the claims, unless otherwise indicated. No phrase herein should be construed as indicating any non-claimed element as essential.

[0031] In general, "substituted" refers to an alkyl, alkenyl, aryl, or ether group, as defined below (e.g., an alkyl group), in which one or more bonds to a hydrogen atom are replaced with a bond to a non-hydrogen or non-carbon atom. Substituted groups also include groups in which one or more bonds to a carbon or hydrogen atom are replaced with one or more bonds, including double or triple bonds, to a heteroatom. Thus, unless otherwise specified, a substituent is substituted with one or more substituents. In some embodiments, a substituent is substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituents include halogens (i.e., F, Cl, Br, and I), hydroxyl, alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups, carbonyl (oxo), carboxyl, ester, urethane, oxime, hydroxylamine, alkoxyamine, aralkoxyamine, thiol, sulfide, sulfoxide, sulfone, sulfonyl, sulfonamide, amine, N-oxide, hydrazine, hydrazide, hydrazone, azide, amide, urea, amidine, guanidine, enamine, imide, isocyanate, isothiocyanate, cyanate, thiocyanate, imine, nitro group, nitrile (i.e., CN), and the like.

[0032] As used herein, "alkyl" groups include straight-chain and branched alkyl groups having 1 to about 20 carbon atoms, typically 1 to 12 carbons, or in some embodiments 1 to 8 carbon atoms. As used herein, "alkyl group" includes cycloalkyl groups, as defined below. Alkyl groups can be substituted or unsubstituted. Alkyl groups may be substituted one or more times. Alkyl groups may be substituted two or more times. Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups, and 1-cyclopentyl-4-methylpentyl groups. Representative substituted alkyl groups may be substituted one or more times, for example, with amino, ammonium, thio, hydroxy, cyano, alkoxy, and / or halo groups, such as F, Cl, Br, and I groups. As used herein, the term haloalkyl is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a perhaloalkyl group.

[0033] Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. In some embodiments, cycloalkyl groups have 3-8 ring members, while in other embodiments the number of ring carbon atoms ranges from 3 to 5, 6, or 7. Cycloalkyl groups can be substituted or unsubstituted. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl, as well as fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups can be mono-, di- or higher substituted, such as, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and / or halo groups.

[0034] Alkenyl groups are straight chain, branched or cyclic alkyl groups having from 2 to about 20 carbon atoms and further containing at least one double bond. In some embodiments, alkenyl groups have from 1 to 12 carbons, or typically from 1 to 8 carbon atoms. Alkenyl groups can be substituted or unsubstituted. Alkenyl groups include, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl groups, among others. Alkenyl groups can be substituted in the same manner as alkyl groups. Divalent alkenyl groups, i.e., alkenyl groups with two points of attachment, include, but are not limited to, CH-CH=CH2, C=CH2, or C=CHCH3.

[0035] As used herein, an "aryl" or "aromatic" group is a cyclic aromatic hydrocarbon that does not contain heteroatoms. Aryl groups include monocyclic, bicyclic, and polycyclic systems. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. Aryl groups having one or more alkyl groups may also be referred to as alkaryl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others 6-12 or 6-10 carbon atoms in the ring portion of the group. The phrase "aryl group" includes groups containing fused rings, such as fused aromatic aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like). The aryl group can be substituted or unsubstituted.

[0036] Heterocyclic or heterocycle refers to both aromatic and non-aromatic cyclic compounds, including monocyclic, bicyclic, and polycyclic rings, containing three or more ring members, where one or more of the ring members is a heteroatom, such as, but not limited to, N, O, and S. Examples of heterocyclic groups are unsaturated 3-8 membered rings containing 1-4 nitrogen atoms, such as pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl, dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl (e.g., 4H-1,2,4-triazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, etc.), tetrazolyl (e.g., 1H-tetrazolyl, 2H tetrazolyl, etc.), etc. saturated 3-8 membered rings containing 1 to 4 nitrogen atoms (such as, but not limited to, pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl, etc.); condensed unsaturated heterocyclic groups containing 1 to 4 nitrogen atoms (such as, but not limited to, indolyl, isoindolyl, indolinyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl, etc.); Unsaturated 3- to 8-membered rings containing 2 oxygen atoms and 1 to 3 nitrogen atoms (such as, but not limited to, oxazolyl, isoxazolyl, oxadiazolyl (e.g., 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, etc.)), saturated 3- to 8-membered rings containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms (such as, but not limited to, morpholinyl), unsaturated condensed heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms (such as, but not limited to, benzoxazolyl, benzoxadiazolyl, benzoxazinyl (e.g., 2H-1,4-benzoxazinyl, etc.)), unsaturated 3- to 8-membered rings containing 1 to 3 sulfur atoms and 1 to 3 nitrogen atoms (such as, but not limited to, thiazolyl, isothiazolyl, thiadiazolyl (e.g., 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,saturated 3-8 membered rings containing 1-2 sulfur atoms and 1-3 nitrogen atoms (such as, but not limited to, thiazolodinyl); saturated and unsaturated 3-8 membered rings containing 1-2 sulfur atoms (such as, but not limited to, thienyl, dihydrodithionyl, dihydrodithionyl, tetrahydrothiophene, tetrahydrothiopyran); unsaturated fused heterocycles containing 1-2 sulfur atoms and 1-3 nitrogen atoms (such as, but not limited to, benzothiazolyl, benzothiadiazolyl, benzothiazinyl (e.g., 2H-1,4-benzothiazinyl), dihydrobenzothiazinyl (e.g., 2H-3,4-dihydrobenzothiazinyl), etc. Heterocyclic groups include, but are not limited to, unsaturated 3-8 membered rings containing an oxygen atom (such as, but not limited to, furyl), unsaturated fused heterocyclic rings containing one or two oxygen atoms (such as, but not limited to, benzodioxolyl (e.g., 1,3-benzodioxoyl), unsaturated 3-8 membered rings containing an oxygen atom and one or two sulfur atoms (such as, but not limited to, dihydrooxathiinyl), saturated 3-8 membered rings containing one or two oxygen atoms and one or two sulfur atoms (such as, but not limited to, 1,4-oxathiane), unsaturated fused rings containing one or two sulfur atoms (such as, benzothienyl, benzodithiinyl), and unsaturated fused heterocyclic rings containing an oxygen atom and one or two oxygen atoms (such as, benzoxathiinyl). Heterocyclic groups also include those mentioned above in which one or more S atoms of the ring are double-bonded to one or two oxygen atoms (sulfoxide and sulfone). For example, heterocyclic groups include tetrahydrothiophene oxide and tetrahydrothiophene 1,1-dioxide. Typical heterocyclic groups contain 5 or 6 ring members. Thus, for example, heterocyclic groups include morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,Examples of heterocyclic groups include 4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl, thiomorpholinyl (wherein the S atom of thiomorpholinyl is bonded to one or more O atoms), pyrrolyl, pyridinylhomopiperazinyl, oxazolidin-2-onyl, pyrrolidin-2-onyl, oxazolyl, quinuclidinyl, thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl. The heterocyclic group or heterocycle may be substituted.

[0037] Heteroaryl groups are aromatic ring compounds containing five or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. Heteroaryl groups include pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, dibenzofuranyl, indolyl, azaindolyl (pyrrolopyridinyl), indazolyl, benzimidazolyl, imidazopyridinyl (azabenzimidinyl), and the like. Heteroaryl groups include, but are not limited to, groups such as pyrazolopyridinyl, triazolopyridinyl, benzotriazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl. Heteroaryl groups include fused ring compounds in which all rings are aromatic (such as indolyl groups), and fused ring compounds in which only one of the rings is aromatic (such as 2,3-dihydroindolyl groups). Although the phrase "heteroaryl group" includes fused ring compounds, the phrase does not include heteroaryl groups having other groups attached to one of the ring members, such as an alkyl group. Rather, heteroaryl groups having such substitutions are referred to as "substituted heteroaryl groups." Representative substituted heteroaryl groups may be substituted one or more times with a variety of substituents such as those listed above.

[0038] As used herein, the prefix "halo" refers to a halogen (i.e., F, Cl, Br, or I) that is bonded to the group that is modified by the "halo" prefix. For example, a haloaryl is a halogenated aryl group.

[0039] Groups described herein that have more than one point of attachment (i.e., divalent, trivalent, or polyvalent) in the compounds of the present technology are indicated by the use of the suffix "ene." For example, a divalent alkyl group is an alkylene group, a divalent aryl group is an arylene group, a divalent heteroaryl group is a divalent heteroarylene group, and so on.

[0040] The present disclosure relates to electrochromic devices incorporating certain phenazine compounds as anodic redox species. As described below, the phenazine compounds disclosed herein are substituted with at least one sterically hindered group (e.g., tertiary butyl group). As shown in the examples, the phenazine compounds described herein are thermally stable and have improved weather resistance, for example, electrical cycling under UV exposure (above about 390 nm). The phenazines described herein are electrochromic.

[0041] More broadly, energy storage devices and / or electrochromic memory devices are disclosed herein that include cathode and anode materials such that when the cathode and anode materials are in an activated state, the device maintains an activated (i.e., dark) state for an extended period of time at open circuit. As the terms cathode and anode materials are used herein, at least one of them is electrochromic. The cathode material / portion may be associated with a first conductive substrate or isolated in a polymer matrix, and the anode material / portion may be associated with a second conductive substrate or isolated in a polymer matrix. For example, the anode material may be covalently crosslinked and coated on a second conductive substrate, and the cathode material may be covalently crosslinked and coated on the surface of a first conductive substrate. By coating the anode and cathode materials on a substrate, the anode and cathode materials are prevented from migrating within the device, and thus the activated state may be maintained indefinitely.

[0042] As mentioned above, the anode or cathode material may also be part of a polymer matrix, with the anode or cathode material being covalently bonded to the polymer. This may be achieved by the presence of functional groups on the anode or cathode material that react with the polymer or monomers that make up the polymer. For example, if the anode or cathode material contains hydroxy groups, the anode or cathode material may be bonded to the polymer matrix by a condensation reaction or react with an isocyanate functionality to form a polyurethane-based polymer matrix. Amines may also react with isocyanate functionality to form urea and biuret bonds. It may also be expected that other crosslinked polymer matrices may be formed using multifunctional epoxies or polymers in combination with curing agents such as amines, alcohols, or anhydrides, or by base- or acid-catalyzed homopolymerization.

[0043] A typical solution-phase electrochromic device contains at least one anodic (easily oxidizable) material or species, at least one cathodic (reducible) material or species, and a solvent. Upon application of a sufficient electrical potential to the solution-phase electrochromic device (i.e., activation), the typical solution-phase device undergoes a color change (i.e., a dark, or low-transmittance state). Because the anodic and cathodic materials are free to diffuse through the solvent while in the activated state, the electrochromic device self-erases when the charging potential is removed. It has been found that isolating the anodic material on the surface of a conductive substrate while isolating the cathodic material on the surface of a second conductive substrate results in an electrochromic device that is configured to maintain a charged, i.e., activated, state for extended periods of time compared to a typical solution-phase electrochromic device, as long as the electrochromic anodic and cathodic films are separated by an ionically conductive electrolyte.

[0044] The electrochromic devices described herein may include at least one chamber defined by a first substrate having a first conductive surface, a second substrate having a second conductive surface, and a sealing member that joins the first substrate to the second substrate with the first and second conductive surfaces in contact with the sealing member. For surface confinement of the anode and cathode materials, the anode material may be isolated on one conductive surface and the cathode material may be isolated on the other conductive surface. An electrolyte is disposed within the chamber between the anode and cathode layers. The first and second substrates may be offset from one another to allow electrical contact to be made at the first and second conductive surfaces as is well established for other solution-phase electrochromic devices.

[0045] In one aspect, an energy storage device or memory device is provided. The energy storage device or memory device may include a cathode material and an anode material. The cathode material may be a viologen and the anode material may be a phenazine as described herein.

[0046] In some embodiments, the anode material comprises a phenazine compound represented by: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 are each independently H, F, Cl, Br, I, CF3, CN, OR 11 , S.R. 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups may be joined to form a monocyclic, polycyclic, or heterocyclic group; Each R 11 are independently H or alkyl; R 5 and R 10 is independent, (i) -L1-A-L2-OR 14 is represented by Each L1 is independently a C1-C8 alkylene group; Each L2 is independently a C1-C8 alkylene group; Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is alkyl or alkylhydroxy, or (ii) -L3-OR 16 is represented by Each L3 is independently a C1-C8 alkylene group; Each R 16 is H or alkyl, R 2 , R3 , R 7 , and R 8 At least one of the groups is a sterically hindering group.

[0047] The steric hindering group may be selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl. The steric hindering group may be an alkyl group that includes an isopropyl moiety. In some embodiments, the steric hindering group is not a methyl group.

[0048] In some embodiments, R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 is independently H. In some embodiments, R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 are each independently H.

[0049] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of R is independently C2-C8 alkyl. 2 , R 3 , R 7 , and R 8 At least one of R is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 2 , R 3 , R 7 , and R 8 At least one of is independently isopropyl, neopentyl, or tertiary butyl.

[0050] In some embodiments, R 2 and R7 , or R 2 and R 8 are each independently C2-C8 alkyl. 2 and R 7 , or R 2 and R 8 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 2 and R 7 , or R 2 and R 8 are each independently isopropyl, neopentyl, or tertiary butyl.

[0051] In some embodiments, R 3 and R 8 , or R 3 and R 7 are each independently C2-C8 alkyl. 3 and R 8 , or R 3 and R 7 are each independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl. 3 and R 8 , or R 3 and R 7 is each independently isopropyl, neopentyl, or tertiary butyl.

[0052] In some embodiments, R 2 , R 3 , R 7 , and R 8 At least one of R is independently aryl. 2 , R 3 , R 7 , and R 8 At least one of is independently phenyl.

[0053] In some embodiments, R 2 and R 7 , or R 2 and R 8 is independently at each occurrence aryl. In some embodiments, R 2 and R 7 are each independently phenyl.

[0054] In some embodiments, R 3 and R 8 , or R 3 and R 7 is independently at each occurrence aryl. In some embodiments, R 3 and R 8 , or R 3 and R 7 Each is independently phenyl.

[0055] In some embodiments, R 5 and R 10 At least one of the -L1-A-L2-OR 14 is represented by each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0056] In some embodiments, each L1 is independently a C2 or C4 alkylene group; each L2 is independently a C3 alkylene group; Each R 14 is H, A is -N(R 15)2 + - is an ammonium group represented by Each R 15 is C1 alkyl or C2 alkyl hydroxyl.

[0057] In some embodiments, R 5 and R 10 At least one of is independently represented by: [ka] n is 1, 2, 3, 4, 5, 6, 7, or 8; x is 1, 2, 3, 4, 5, 6, 7, or 8; Each R 15 is independently C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0058] In some embodiments, n is 2 or 4; x is 3, Each R 15 is independently C1 alkyl or C2 alkyl hydroxyl.

[0059] In some embodiments, R 5 and R 10 At least one of the -L3-OR 16 is represented by each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 16 is H or alkyl.

[0060] In some embodiments, each L3 is independently a C4 or C6 alkylene group; Each R 16 is H.

[0061] In some embodiments, R 5 and R 10 At least one of is independently represented by: [ka] y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0062] In some embodiments, y is 3 or 6.

[0063] In some embodiments, the compound is F - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6 - , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , Al(OC(CF3)3)4 - , BAr4 - or a mixture of anions thereof, where Ar is an aryl group or a fluorinated aryl group. In some embodiments, the anion is PF6 - , SO3CF3 - and mixtures of these anions.

[0064] According to various embodiments herein, the phenazine compounds disclosed herein can be any one of the following compounds: As noted above, some of the disclosed phenazines have at least one net positive charge that is electronically balanced by an anion (not shown). The anion can be any of the various anions described above. [ka] [ka] [ka] [ka]

[0065] In another aspect, an electrochromic device includes an anode material coated and covalently crosslinked on the surface of a first conductive substrate, and a cathode material coated and covalently crosslinked on the surface of a second conductive substrate. The electrochromic device exhibits a high transmission state upon short circuit and a low transmission state upon application of a potential, the high transmission state being at least four times greater than the low transmission state, and the electrochromic device is configured to maintain within 5% of the transmission of the low transmission state at 20° C. in an open circuit for at least 8 hours after application of a potential sufficient to reach the low transmission state. In some embodiments, the electrochromic device is configured to maintain within 5% of the transmission of the low transmission state at 20° C. in an open circuit for at least 8, 10, 15, 20, 24, or 48 hours after application of a potential sufficient to reach the low transmission state. In some embodiments, the device is configured to maintain within 10% of the transmission of the low transmission state at 20° C. in an open circuit for at least 2, 3, 4, or 5 days after application of a potential sufficient to reach the low transmission state. In some embodiments, the device is configured to maintain a transmittance within 10% of the low transmittance state at 20° C. in open circuit for 8 hours to 10 days after application of a potential sufficient to reach the low transmittance state. The low transmittance state can range from about 0.001% to about 30%. The high transmittance state ranges from about 50% to about 95%. In some embodiments, after 4000 cycles from the high transmittance state to the low transmittance state, the high transmittance value does not change by more than 5% from the initial high transmittance value. As used herein, the initial high transmittance value is the state of the device after device fabrication and prior to application of a potential. In some embodiments, after 4000 cycles from the high transmittance to the low transmittance state, the low transmittance value does not change by more than 5% from the initial low transmittance value. As used herein, the initial low transmittance value is the low transmittance value achieved by the first charge of the device at full voltage application.

[0066] In any of the above embodiments, the cathode material may be a viologen, a low dimer viologen, or a non-dimer viologen. The term low dimer viologen applies to some viologens that exhibit dimerization characteristics to a lesser extent than dimer viologen. The viologen material may be physically trapped inside and sequestered in a polymer matrix, or functionalized to accept the viologen material being polymerized or reacted with a polymer so as to be covalently bonded to the polymer. Exemplary viologens include, but are not limited to, methyl viologen, octyl viologen, benzyl viologen, polymerized viologen, and viologens described in U.S. Patent Nos. 4,902,108, 6,188,505, 5,998,617, 10,464,900, and 6,710,906. The other viologens may include those of formula (I), (III), or (IV). Formula (I): [ka] In formula I, R 1 and R 2 is independently alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl; R 4 , R 6 , R 8 and R 10 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 3 , R 5 , R 7 , and R 9 are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and X is an anion, provided that formula (I) includes 3 and R 5 , or R 7 and R 9 , or R 3 , R 5 , R 7 , and R 9 may be individually specified to be a secondary alkyl, a tertiary alkyl, or an aryl. Formula (III): [ka] In formula (III), R 1 and R 2 is independently alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl; R 4 , R 6 , R 8 , R 10 are independently H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R 3 , R 5 , R 7 , and R 9 are independently H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl; R 19 is (CH2) n’ or arylene, n' is 1 to 12, X is an anion, and R 3 and R 5 , or R 7 and R 9 is individually a secondary alkyl, a tertiary alkyl, or an aryl. Formula (IV): [ka] In formula (IV), R 1 and R 1’ is independently alkyl, siloxyalkyl, hydroxyalkyl, alkenyl, or aralkyl; R 4 , R 6 , R 8 , R 10 , R 4’ , R 6’ , R 8’ , and R 10’ are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 7 , R 9 , R 7’ , and R 9’are individually H, OH, F, Cl, Br, I, CN, NO2, alkyl, alkoxy, or aryl, and R 19 (CH2) n’ or arylene, n' is 1 to 12, X is an anion, and R 3 , R 5 , R 3’ , and R 5’ is individually a secondary alkyl, a tertiary alkyl, or an aryl, or R 7 , R 9 , R 7’ , and R 9’ are individually secondary alkyl, tertiary alkyl, or aryl. For any of the viologens listed, the counterion (anion) can be any of the following: halide, borate, fluoroborate, tetraarylborate, hexafluorometal or metalloid, sulfate, sulfonate, sulfonamide, carboxylate, perchlorate, tetrachloroferrate, etc., or a mixture of any two or more thereof. Exemplary counterions / anions include, but are not limited to, F - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6 - , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , or BAr4 - where Ar is an aryl or fluorinated aryl or bis(trifluoromethyl)aryl group. In some embodiments, X is a tetrafluoroborate or bis(trifluoromethylsulfonyl)imide anion.

[0067] In any of the above aspects, the anode material may be any one or more of the phenazine compounds described herein covalently bonded to or confined within a second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the activated anode material. For viologens, the anode material may be sequestered within the polymer matrix by being physically trapped therein, or the anode material may be polymerized or functionalized to accept reaction with a polymer such that it is covalently bonded to the polymer.

[0068] Further examples of anode and cathode materials can be found in U.S. Patent Nos. 4,902,108, 5,294,376, 5,998,617, 6,193,912, 10,971,718, and 8,228,590.

[0069] If the device includes an electrolyte, the electrolyte may include a solvent and a salt. The salt may be a metal salt or an ammonium salt. Exemplary solvents used in the electrolyte may include, but are not limited to, 3-methylsulfolane, dimethylsulfoxide, dimethylformamide, tetraglyme, and other polyethers, alcohols such as ethoxyethanol, nitriles such as acetonitrile, glutaronitrile, 3-hydroxypropionitrile, and 2-methylglutaronitrile, ketones including 2-acetylbutyrolactone and cyclopentanone, cyclic esters including β-propiolactone, γ-butyrolactone, and γ-valerolactone, propylene carbonate (PC), ethylene carbonate, and homogeneous mixtures thereof. Although specific solvents are disclosed in connection with the electrolyte, numerous other solvents known to those skilled in the art having this disclosure prior to them are contemplated for use as well. Exemplary salts include, but are not limited to, Li + , Na + , K + , NR'4 +and the like, but are not limited to, metal or ammonium salts, where each R' is independently selected from the group consisting of F. - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6 - , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , Al(OC(CF3)3)4 - , or BAr4 - where Ar is an aryl or fluoroaryl group such as, but not limited to, C6H5, 3,5-(CF3)2C6H3]4, or C6F5. Further examples of polymer electrolyte materials for use in electrochromic devices can be found in U.S. Patent Nos. 6,635,194 and 5,940,201.

[0070] With regard to the substrate and the conductive coating thereon, those commonly used in solution-based electrochromic devices may be used. For example, one or both substrates may be glass, metal, plastic, or ceramic. The conductive coating on one or more substrates may be transparent or opaque depending on the intended use of the device. For example, if the device is a window, both coatings should be substantially transparent, and if the device is a mirror, at least one coating is transparent. Exemplary transparent conductive materials include, but are not limited to, fluorine-doped tin oxide (FTO), indium / tin oxide (ITO), doped zinc oxide, indium zinc oxide, metal oxide / Ag / metal oxide, silver nanowire coatings, carbon nanotubes, graphene coatings, wire grids, conductive polymers such as, but not limited to, poly(3,4-ethylenedioxythiophene) (PEDOT). Non-transparent conductive coatings include metal coatings such as rhodium, chromium, nickel, silver, gold, and other metals, or mixtures of any two or more thereof.

[0071] The invention having thus been generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to limit the invention. EXAMPLES

[0072] Working Example

[0073] Example 1. Synthesis of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium hexafluorophosphate.

[0074] The four step synthesis of the title compound is as follows. Step 1: 2,7(8)-Di-tert-butyl-5,10-dihydrophenazine (as a mixture of two isomers) [ka] Step 2: 4-Bromo-N-(3-hydroxypropyl)-N,N-dimethylbutan-1-aminium bromide [ka] Step 3: N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide [ka] Step 4: Metathesis to PF6 salt [ka]

[0075] Step 1: 400.0 g of 4-(tert-butyl)benzene-1,2-diamine, 992 g of 4-(tert-butyl)benzene-1,2-diol, and 1330 mL of ethylene glycol were added to a three-necked 5 L round-bottom flask equipped with a Dean-Stark condenser, mechanical stirrer, and thermometer. The mixture was heated to 203 °C under nitrogen atmosphere for one week. The reaction mixture was then cooled to 60 °C. The solid was filtered under inert conditions to prevent oxidation. The solid was then washed with a 1:1 mixture of acetone and water (4 L). The solid was recrystallized by first partially dissolving in 1 L acetone, then adding aqueous sodium dithionite (160 g was dissolved in 2 L of water). Finally, the solution was cooled to room temperature and the solid was filtered under inert conditions. Removal of the solvent in vacuum afforded 516 g (72% yield) of 2,7-di-tert-butyl-5,10-dihydrophenazine. GC analysis showed 99.8% pure product.

[0076] Step 2: A 12 liter round bottom flask was charged with 1,4-dibromobutane (2260 g) and acetone (6 L). The flask was cooled to 5-7°C. Dimethylaminopropanol (1200 g) was added slowly via addition funnel. The reaction was slightly exothermic. Once the addition was complete, the temperature was allowed to rise to room temperature. After stirring at room temperature for 48 hours, the product precipitated as white crystals. The solid product was filtered and washed with acetone. Vacuum drying afforded 3112 g of the desired product (93% yield).

[0077] Step 3: 240 g of 2,7-di-tert-butyl-5,10-dihydrophenazine, 1154 g of 4-bromo-N-(3-hydroxypropyl)-N,N-dimethylbutan-1-aminium bromide, 280 g of sodium dithionite, 375 g of sodium carbonate, 30 g of methyltributylammonium chloride, 30 mL of water, and 7400 mL of acetonitrile were added to a 12 L round bottom flask. The mixture was heated to reflux under nitrogen for 48 hours, and HPLC analysis showed no presence of dihydrophenazine. 3 L of acetonitrile was then distilled off, the reaction mixture was allowed to cool to room temperature, and the reaction solid was then filtered and washed with 2.5 L of acetone. The solid was redissolved in 1.3 L of water and heated to distill off the residual acetone at 70° C. 2 L of ethanol was added and the reaction mixture was allowed to cool to room temperature. The solid was filtered and washed with ethanol. The solids were discarded and the filtrate containing the product was concentrated in vacuo to an oil. The oil was added to 6 L of warm acetone. After cooling, the filtrate was decanted and the gummy solid was washed with additional acetone. The gummy solid was N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide and was used directly to make the PF6 salt. The product was 99% pure by HPLC and mass ES analysis. Step 4: Synthesis of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium hexafluorophosphate.

[0078] First metathesis: The gummy solid of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide was dissolved in a mixture of 900 mL water and 100 mL triethylamine by heating to 50° C. 2500 mL of 30% aqueous NH4PF6 was added and the reaction was stirred at 50° C. for 5 hours. Upon cooling the reaction, N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium hexafluorophosphate precipitated as a gray solid in 720 g of wet solid.

[0079] The second metathesis was repeated by dissolving the solid in 350 mL of acetonitrile, 1000 mL of water, 150 mL of triethylamine, and 1000 mL of ethanol. The reaction mixture was heated to 65° C. and 1700 mL of 30% NH4PF6 solution was added. Heating was continued for 3 hours, and then 1000 mL of water was added. 150 mL of acetonitrile was distilled off and the reaction was cooled to room temperature. Upon cooling, the product solidified. The filtrate was decanted and the product was washed with 3 L of cold water to give a gummy solid. The solid was dissolved in 1000 mL of acetonitrile. The acetonitrile and residual water were completely removed under vacuum to give a brown concentrate. To the brown concentrate was added a hot solution mixture of 4000 mL of ethanol, 100 mL of triethylamine, and 10 mL of anhydrous hydrazine. Heating was continued at 60° C. for 15 minutes, and then the reaction was cooled to 40° C. and 2000 mL of hexane was added. The reaction was cooled to room temperature and then cooled to 0-5 °C for 4 h. The solid was filtered under inert conditions and washed with 1000 mL of cold ethanol, then 1000 mL of a 1:1 mixture of ethanol and hexane. The solid was dried under vacuum to give 494 g (64% yield) of an off-white solid. The product is 99.5% pure by HPLC and mass spectrometry.

[0080] Example 2. Synthesis of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium triflate:

[0081] 50 g of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bromide was dissolved in 85 mL of warm water and 250 mL of 30% sodium triflate was added. The reaction mixture was heated to 60° C. for 4 hours. 200 mL of water was added followed by cooling to room temperature. The product was filtered and washed with 300 mL of water under inert conditions.

[0082] The second metathesis was carried out by dissolving the above solid in 150 mL of warm water. 20 mL of triethylamine was added. The reaction was stirred at 50° C. for 5 hours. The reaction was cooled and filtered to give 50 g (82% yield) of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium triflate as a white solid after drying under vacuum. The product was 99.9% pure by HPLC and mass spectrometry.

[0083] Example 3. Formulations and processes for preparing phenazine-based devices

[0084] In this example, Device A was made with the following compounds: [ka]

[0085] In this example, Device B was made with the following compounds: [ka]

[0086] Device A was prepared by coating a 3 inch by 3 inch piece of indium tin oxide (ITO) coated glass (2.2 mm thick) with a mixture made by dissolving 0.3518 grams of bisN,N'-(6-hydroxyhexyl) viologen bis[bistrifluoromethanesulfonylimide] (NTF), 0.0149 grams of octamethylbis(6-hydroxyhexyl)ferrocenium bis(tetrafluoroborate), 0.0006 grams of surfactant (TEGO Glide 410), and 0.1433 grams of HDT-isocyanurate (Desmodur N3300, Covestro) in 3 grams of a solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35 wt% PC, 65 wt% MPN) with 100 ppm of dibutyltin diacetate (DBTDA) catalyst. The mixture was coated directly onto the ITO coating with a #16 Mayer rod to control the thickness.

[0087] For device A, a second piece of 3" x 3" ITO coated glass (2.2 mm thick) was also coated with a solution made by dissolving 0.3969 grams of 5,10-bis(n-butyl-N,N-dimethylammonium n-propanol)phenazine triflate, 0.0166 grams of octamethylbis(6-hydroxyhexyl)ferrocene, 0.0006 grams of surfactant (TEGO Glide 410) and 0.1866 grams of HDT-isocyanurate (Desmodur N3300, Covestro) in 3 grams of a solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% by weight PC, 65% by weight MPN) with 100 ppm of DBTDA catalyst. A second film was made by coating the solution with a #8 Mayer rod to control the thickness.

[0088] Device B was prepared by coating a 3" x 3" piece of indium tin oxide (ITO) coated glass (2.2 mm thick) with a solution made by dissolving 0.3588 grams of bis(6-hydroxyhexyl) viologen bis[bistrifluoromethanesulfonylimide] (NTF), 0.0149 grams of octamethyldihexanol ferrocenium bis(tetrafluoroborate), 0.0006 grams of surfactant (TEGO Glide 410), and 0.1433 grams of HDT-isocyanurate (Desmodur N3300, Covestro) in 3 grams of a solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN) with 100 ppm of dibutyltin diacetate (DBTDA) catalyst. The film was made by coating the solution with a #16 Mayer rod to control the thickness.

[0089] and for Device B, 0.4112 grams of N-butyl-4-(2,7-di-tert-butyl-10-(4-((3-hydroxypropyl)dimethylammonio)butyl)phenazin-5(10H)-yl)-N,N-dimethylbutan-1-aminium bis(hexafluorophosphate), 0.0152 grams of octamethylbis(6-hydroxyhexyl)ferrocene, 0.0006 grams of surfactant (TEGO Glide 410), and 0.1706 grams of HDT-isocyanurate (Desmodur A second piece of 3" x 3" ITO coated glass (2.2 mm thick) was coated with a solution of 100 ppm DBTA in 3 grams of a solution of propylene carbonate (PC) and 3-methoxypropionitrile (MPN) (35% PC, 65% MPN) containing N3300 (Covestro), thereby forming a second film. This second film was made with a #8 Mayer rod.

[0090] The above films were cured overnight in a 60°C oven under nitrogen atmosphere. Once the films were cured, the edges of the films were removed (less than 1 centimeter) to accommodate the epoxy seal and electrical contacts to the ITO. The first and second films on each ITO-coated glass substrate were positioned in a spaced-apart relationship facing each other, and an epoxy seal was placed around the perimeter and cured to form a cell leaving an offset for attachment of electrical contacts. The distance between the two substrates was approximately 135 micrometers. The resulting cell was filled with a solution of 0.1 molar tetraethylammonium bis-trifluoromethanesulfonimidate (TEANTF) in PC and a crosslinkable polymer matrix precursor to form a gel electrolyte.

[0091] Devices A and B, having two different anode chemistries, were subjected to various durability tests.

[0092] The results of the UV cycle durability test for devices A and B are shown in Figure 1. The devices were equipped with a xenon lamp weather meter (0.55 W / m at 340 nm). 2 The devices were exposed to a 3000 hour UV-induced IR (Atlas Weather-Ometer) at 1000 Hz. Devices A and B were tested behind an optical attenuator made by laminating two sheets of Kuraray UV extra protect PVB film (Trosifol®) and one sheet of 3M™ Ultraclear Solar IR reflective film between two sheets of soda-lime glass (one 1.1 mm thick and one 2.2 mm thick). The cycling profile for both devices was 3 hours in the dark and 1 hour in the clear state. Device A was cycled between the clear state (0 volts) and the completely dark state (0.8 volts), while Device B was cycled between the clear state (0 volts) and the completely dark state (0.7 volts). The delta E for UV cycling of Device B after 4000 hours was only 13.9, while Device A showed significant color change with a delta E of 30.

[0093] Device B, fabricated with a phenazine compound having a tert-butyl group, showed a significant improvement in UC cycling durability, as shown in FIG.

[0094] The results of 85° C. cycling durability testing of Devices A and B are shown in Figure 2. The cycling profile for both devices was 3 hours in the dark and 1 hour in the clear state. Device A was cycled between the clear state (0 volts) and the completely dark state (0.8 volts), while Device B was cycled between the clear state (0 volts) and the completely dark state (0.7 volts).

[0095] Item 1: A compound represented by: [ka] During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 are each independently H, F, Cl, Br, I, CF3, CN, OR 11 , S.R. 11 , NO2, alkyl, alkoxy, aryl, heteroaryl, amino, ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups may be joined to form a monocyclic, polycyclic, or heterocyclic group; Each R 11 are independently H or alkyl; R 5 and R 10 is independent, (i) -L1-A-L2-OR 14 is represented by Each L1 is independently a C1-C8 alkylene group; Each L2 is independently a C1-C8 alkylene group; Each R14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is alkyl or alkylhydroxy, or (ii) -L3-OR 16 is represented by Each L3 is independently a C1-C8 alkylene group; Each R 16 is H or alkyl, R 2 , R 3 , R 7 , and R 8 at least one of which is a sterically hindering group.

[0096] Item 2. The compound of item 1, wherein the sterically hindering groups are selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

[0097] Section 3 R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 3. The compound of claim 1 or 2, wherein each is independently H.

[0098] Section 4 R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 3. The compound of claim 1 or 2, wherein each is independently H.

[0099] Section 5 R 2 , R 3 , R 7 , and R 8 At least one of the following is independently a C2 to C8 alkyl group:

[0100] Section 6 R 2 , R 3 , R 7 , and R 8 6. The compound of claim 5, wherein at least one of is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0101] Section 7 R 2 , R 3 , R 7 , and R 8 7. The compound according to claim 6, wherein at least one of is independently isopropyl, neopentyl, or tertiary butyl.

[0102] Section 8 R 2 and R 7 , or R 2 and R 8 are each independently a C2 to C8 alkyl.

[0103] Section 9 R 2 and R 7 , or R 2 and R 8 is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0104] Section 10 R 2 and R 7 , or R 2 and R 8 10. The compound according to clause 9, wherein each is independently isopropyl, neopentyl, or tertiary butyl.

[0105] Section 11 R 3 and R 8 , or R 3 and R 7are each independently a C2 to C8 alkyl.

[0106] Section 12 R 3 and R 8 , or R 3 and R 7 12. The compound of claim 11, wherein each is independently ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, or octyl.

[0107] Section 13 R 3 and R 8 , or R 3 and R 7 13. The compound according to claim 12, wherein each is independently isopropyl, neopentyl, or tertiary butyl.

[0108] Section 14 R 2 , R 3 , R 7 and R 8 At least one of the following is independently aryl:

[0109] Section 15 R 2 , R 3 , R 7 and R 8 15. The compound according to claim 14, wherein at least one of is independently phenyl.

[0110] Section 16 R 2 and R 7 , or R 2 and R 8 are each independently aryl.

[0111] Section 17 R 2 and R 7 17. The compound according to clause 16, wherein each is independently phenyl.

[0112] Section 18 R3 and R 8 , or R 3 and R 7 Each of the following is independently aryl:

[0113] Section 19 R 3 and R 8 , or R 3 and R 7 20. The compound according to claim 18, wherein each is independently phenyl.

[0114] Section 20 R 5 and R 10 at least one of is independently represented by: -L1-A-L2-OR 14 each L1 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; each L2 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 14 is H or alkyl, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0115] Section 21 each L1 is independently a C2 or C4 alkylene group; each L2 is independently a C3 alkylene group; Each R 14 is H, A is -N(R 15 )2 + - is an ammonium group represented by Each R 15 is C1 alkyl or C2 alkyl hydroxyl.

[0116] Section 22 R 5 and R 10 at least one of is independently represented by: [ka] n is 1, 2, 3, 4, 5, 6, 7, or 8; x is 1, 2, 3, 4, 5, 6, 7, or 8; Each R 15 is independently C1-C8 alkyl or C1-C8 alkylhydroxyl.

[0117] Section 23 n is 2 or 4; x is 3, Each R 15 is independently C1 alkyl or C2 alkyl hydroxyl.

[0118] Section 24 R 5 and R 10 at least one of is independently represented by: -L3-OR 16 each L3 is independently a C1, C2, C3, C4, C5, C6, C7, or C8 alkylene group; Each R 16 20. The compound according to any one of items 1 to 19, wherein is H or alkyl.

[0119] Section 25 each L3 is independently a C4 or C6 alkylene group; Each R 16 25. The compound according to claim 24, wherein

[0120] Section 26 R 5 and R 10 at least one of is independently represented by: [ka] 20. The compound according to any one of items 1 to 19, wherein y is 1, 2, 3, 4, 5, 6, 7, or 8.

[0121] Section 27 27. The compound according to paragraph 26, wherein y is 3 or 6.

[0122] 28. The compound is F - , Cl - , Br - , I - , BF4 - , PF6 - , SbF6 - , AsF6 - , ClO4 - , SO3CF3 - , N(CF3SO2)2 - , C(CF3SO2)3 - , N(SO2C2F5)2 - , Al(OC(CF3)3)4 - , BAr4 - 24. The compound according to any one of items 1 to 23, wherein Ar is an ammonium salt having an anion comprising:

[0123] Item 29: The anion is PF6 - and SO3CF3 - 29. The compound according to claim 28, selected from:

[0124] Item 30. The compound of item 1, wherein the compound is selected from the following: [ka] [ka] [ka] [ka]

[0125] Section 31 Energy storage device, A cathode material; an anode material; the cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, the first polymer matrix being configured to prevent or minimize substantial diffusion of the cathode material; 31. An energy storage device, wherein an anode material comprises the phenazine compound of any one of claims 1 to 30 covalently bonded to or confined within a second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the anode material.

[0126] Section 32 Energy storage device, a first cell including an anode material; a second cell including a cathode material; a porous separator separating the first cell from the second cell; The anode material comprises the phenazine compound according to any one of claims 1 to 30, An energy storage device, wherein the cathode material comprises a viologen.

[0127] Item 33. The energy storage device of item 31 or 32, further comprising a solvent and an electrolyte comprising a metal salt or an ammonium salt.

[0128] Clause 34. The energy storage device of clause 32 or clause 33, wherein the separator comprises an ion exchange membrane or a size exclusion membrane.

[0129] Item 35. The energy storage device according to any one of items 31 to 34, wherein the energy storage device is a battery.

[0130] Although particular embodiments have been illustrated and described, it should be understood that changes and modifications can be made in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0131] The embodiments illustratively described herein may be suitably practiced in the absence of any element or elements, or limitation or limitations not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," and the like, are to be read expansively and without limitation. Furthermore, the terms and expressions used herein are used in a descriptive sense and not in a limiting sense, and in using such terms and expressions, it is not intended to exclude any equivalents of the features shown and described, or portions thereof, and it is recognized that various modifications are possible within the scope of the claimed technology. It is also to be understood that the phrase "consisting essentially of" includes the elements specifically recited, and additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0132] The present disclosure is not limited in terms of the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to the methods and compositions recited herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the above. Such modifications and variations are intended to be within the scope of the appended claims. The present disclosure is limited only in terms of the appended claims, and the full scope of equivalents to such claims. It will be understood that the present disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which may, of course, vary. It will also be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0133] Furthermore, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is also described in terms of any individual members or subgroups of members of the Markush group.

[0134] As will be apparent to one of ordinary skill in the art, for all purposes, particularly in terms of providing a description, all ranges disclosed herein encompass all possible subranges and combinations of subranges. It can be easily recognized that a recited range fully describes and allows for the same range to be divided into at least 1 / 2, 1 / 3, 1 / 4, 1 / 5, 1 / 10, etc. As a non-limiting example, each range described herein can be easily divided into a lower 1 / 3, a middle 1 / 3, and an upper 1 / 3, etc. As will also be apparent to one of ordinary skill in the art, all phrases such as "up to," "at least," "greater than," "less than," etc., include the recited numbers and refer to ranges that can be subsequently divided into subranges as described above. Finally, as will be apparent to one of ordinary skill in the art, a range includes each individual member.

[0135] All publications, patent applications, issued patents, and other documents mentioned herein are incorporated by reference in their entirety herein as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the documents incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0136] Other embodiments are set forth in the following claims.

Claims

1. A compound represented by: 【Chemistry 1】 During the ceremony, R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 are each independently H, F, Cl, Br, I, or CF 3 , C.N., OR 11 , S.R. 11 , NO 2 , alkyl, alkoxy, aryl, heteroaryl, amino, or ammonium, or R 3 , R 4 , R 8 , and R 9 Any two adjacent groups may be joined to form a monocyclic, polycyclic, or heterocyclic group; Each R 11 are independently H or alkyl; R 5 and R 10 is independent, -L 1 -AL 2 -OR 14 is represented by Each L 1 is independent, C 1 ~C 8 is an alkylene group, Each L 2 is independent, C 1 ~C 8 is an alkylene group, Each R 14 is H or alkyl, A is -N(R 15 ) 2 + - is an ammonium group represented by Each R 15 is alkyl or alkylhydroxy, or -L 3 -OR 16 is represented by Each L 3 is independent, C 1 ~C 8 is an alkylene group, Each R 16 is H or alkyl, R 2 , R 3 , R 7 , and R 8 at least one of which is a sterically hindering group.

2. 2. The compound of claim 1, wherein the sterically hindering groups are selected from tertiary butyl, isobutyl, isopropyl, 2-ethylbutyl, 2-ethylhexyl, sec-butyl, isopentyl, and neopentyl.

3. R 1 , R 3 , R 4 , R 6 , R 8 , and R 9 The compound of claim 1 , wherein each is H.

4. R 1 , R 3 , R 4 , R 6 , R 7 , and R 9 The compound of claim 1 , wherein each is H.

5. R 2 , R 3 , R 7 , and R 8 At least one of the 2 ~C 8 The compound of claim 1 , wherein the aryl group is an alkyl group.

6. R 2 and R 7 , or R 2 and R 8 are each independently, C 2 ~C 8 The compound of claim 1 , wherein the aryl group is an alkyl group.

7. R 3 and R 8 , or R 3 and R 7 are each independently, C 2 ~C 8 The compound of claim 1 , wherein the aryl group is an alkyl group.

8. R 2 , R 3 , R 7 , and R 8 2. The compound of claim 1, wherein at least one of is independently aryl.

9. R 5 and R 10 At least one of the following is independently -L 1 -AL 2 -OR 14 is represented by Each L 1 is independent, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , or C 8 is an alkylene group, Each L 2 is independent, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , or C 8 is an alkylene group, Each R 14 is H or alkyl, A is -N(R 15 ) 2 + - is an ammonium group represented by Each R 15 is C 1 ~C 8 Alkyl or C 1 ~C 8 The compound of claim 1 which is an alkyl hydroxyl.

10. Each L 1 is independent, C 2 or C 4 is an alkylene group, Each L 2 is independent, C 3 is an alkylene group, Each R 14 is H, A is -N(R 15 ) 2 + - is an ammonium group represented by Each R 15 is C 1 Alkyl or C 2 10. The compound of claim 9 which is an alkyl hydroxyl.

11. R 5 and R 10 At least one of is independently represented by: 【Chemistry 2】 n is 1, 2, 3, 4, 5, 6, 7, or 8; x is 1, 2, 3, 4, 5, 6, 7, or 8; Each R 15 is independent, C 1 ~C 8 Alkyl or C 1 ~C 8 The compound of claim 1 which is an alkyl hydroxyl.

12. n is 2 or 4; x is 3, Each R 15 is independent, C 1 Alkyl or C 2 12. The compound of claim 11 which is an alkyl hydroxyl.

13. R 5 and R 10 At least one of the following is independently -L 3 -OR 16 is represented by Each L 3 is independent, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , or C 8 is an alkylene group, Each R 16 is H or alkyl.

14. R 5 and R 10 At least one of is independently represented by: 【Chemistry 3】 2. The compound of claim 1, wherein y is 1, 2, 3, 4, 5, 6, 7, or 8.

15. The compound is F - , Cl - , Br - , I - , B.F. 4 - , P.F. 6 - , SbF 6 - , AsF 6 - , ClO 4 - , S.O. 3 CF 3 - , N(CF 3 SO 2 ) 2 - , C(CF 3 SO 2 ) 3 - , N(SO 2 C 2 F 5 ) 2 - , Al(OC(CF 3 ) 3 ) 4 - , BAr 4 - or a mixture of such anions, where Ar is an aryl group or a fluorinated aryl group.

16. 2. The compound of claim 1, wherein the compound is: 【Chemistry 4-1】 【Chemistry 4-2】 【Chemistry 4-3】 【Chemistry 4-4】 【Chemistry 4-5】

17. 1. An energy storage device, comprising: A cathode material; an anode material; the cathode material comprises a viologen covalently bonded to or confined within a first polymer matrix, the first polymer matrix being configured to prevent or minimize substantial diffusion of the cathode material; 13. An energy storage device, wherein the anode material comprises the phenazine compound of claim 1 covalently bonded to or confined within a second polymer matrix, the second polymer matrix being configured to prevent or minimize substantial diffusion of the anode material.

18. 1. An energy storage device, comprising: a first cell including an anode material; a second cell including a cathode material; a porous separator separating the first cell from the second cell; The anode material comprises a compound according to any one of claims 1 to 16, The energy storage device, wherein the cathode material comprises a viologen.

19. 20. The energy storage device of claim 17, further comprising an electrolyte comprising a solvent and a metal salt or an ammonium salt.

20. 20. The energy storage device of claim 17, wherein the separator comprises an ion exchange membrane or a size exclusion membrane.

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