Electrochromic devices and compositions including anode component anions

Abstract

The present invention relates to electrochromic devices and compositions wherein the anode component thereof comprises anode component anions selected from at least one anode component anion represented by the following formula (I) or (II): # imgabs0 # with respect to formulae (I) and (II), R1 and R2 are each independently selected from a divalent linear or branched alkane linking group. In relation to formula (II), R3 is selected from fluorine, a linear or branched fluorinated alkyl group or a linear or branched perfluorinated alkyl group. The invention also relates to a salt comprising an anion represented by formula (II). The invention further relates to neutral compounds corresponding to formula (II), wherein hydrogen (H) is bonded to a nitrogen anion.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application has and claims priority to U.S. Provisional Patent Application No. 63 / 333,182 filed on April 21, 2022 and U.S. Non-Provisional Patent Application No. 18 / 133,559 filed on April 12, 2023, the disclosures of which are incorporated herein by reference in their entirety in each case. Technical Field

[0002] The present invention relates to electrochromic devices and compositions comprising an anode component anion, wherein the anion is covalently bonded to the anode component or group. Background Art

[0003] Electrochromism involves a reversible change in the visible color and / or visible light transmittance of a material under the application of an electrical potential. The change in color and / or transmittance typically involves alternating cycles of oxidized and reduced charge states. Typically, materials that produce color when undergoing reduction are referred to as cathodically coloring electrochromic materials; and materials that produce color when undergoing oxidation are referred to as anodically coloring electrochromic materials.

[0004] Electrochromic devices typically include opposing electrodes (e.g., anodes and cathodes) with a solution- or gel-based electrochromic layer interposed therebetween. The dynamics of such electrochromic devices are typically controlled primarily by mass transport of cathode components and anode components across and through the electrochromic layer. For the purpose of charge conversion, the currents of the two electrodes must be equal. If one component (cathode or anode component) moves or is transported through or across the electrochromic layer more slowly, a higher concentration of the component is typically required, and more particularly, a higher concentration gradient (higher interface concentration) of the slower moving / transported component at the electrode interface is required to balance the diffusion flux and maintain a given current. Adjusting and / or maintaining a higher concentration of a component with reduced mass transport may require additional preparation and / or manufacturing steps, and may cause unintentional blending errors. In some cases, an unbalanced mass transport may cause a reduction in the durability of the electrochromic device, especially when the active component that is more slowly mass transported undergoes over-oxidation or over-reduction at a particular electrode.

[0005] Factors that contribute to reduced mass transport of components and, accordingly, mass transport imbalance between components include, but are not limited to, reduced solubility of the component in the electrochromic layer and / or lack of charge associated therewith. In some electrochromic devices, the cathode component has a positive charge and has a counter anion associated therewith, while the anode component does not have a charge associated therewith. Lack of charge associated with the anode component can contribute to an undesirable mass transport imbalance associated with the cathode component.

[0006] There is a need to develop new electrochromic devices and compositions wherein the active components thereof, and in particular the cathode and anode components, provide an improved mass transport balance. There is also a need for such newly developed electrochromic devices and compositions to provide or otherwise have associated therewith improved durability, reduced manufacturing and / or operating costs, and / or improved operating efficiency. Summary of the invention

[0007] According to the present invention, an electrochromic device is provided, which comprises: (a) a first substrate having a surface comprising a first transparent electrode layer; (b) a second substrate having a surface comprising a second transparent conductive electrode layer, wherein the first transparent electrode layer and the second transparent electrode layer are spaced apart from each other; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent conductive electrode layer. The electrochromic layer comprises: (i) a cathode component; and (ii) an anode component, which comprises an anode component anion selected from at least one anode component anion represented by the following formula (I) or formula (II), Regarding formula (I), R 1 is selected from divalent straight or branched alkane linking groups. 2 is selected from divalent straight or branched alkane linking groups, and R 3 is selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl. The electrochromic layer further comprises: (iii) an optional electrolyte; and (iv) a polymer matrix.

[0008] According to the present invention, there is also provided an electrochromic composition comprising: (i) a cathode component; (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by formula (I) or formula (II) as described above; (iii) an optional electrolyte; (iv) a polymeric thickener; and (v) a solvent.

[0009] Also according to the present invention, there is provided a compound represented by the following formula (IIa), Regarding formula (IIa), R 2 is selected from a divalent straight or branched alkane linking group; and R 3 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

[0010] According to the present invention, there is also provided a salt comprising an anion represented by the following formula (II), Regarding formula (II), R2 is selected from a divalent straight or branched alkane linking group; and R 3 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

[0011] The features and particularities which characterize the invention are pointed out in the claims which are annexed to and form a part of this disclosure. These and other features of the invention, its operating advantages and specific objects attained by its use will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are illustrated and described. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is a representative side elevation cross-sectional view of an electrochromic device according to the present invention; and

[0013] Figure 2 is a graphical representation of the percent transmission versus wavelength obtained by an electrochromic device according to the present invention in the activated (dark) and unactivated (transparent) states, as described in the Examples herein.

[0014] exist Figure 1 and Figure 2 Unless otherwise stated, similar features always refer to the same components and / or elements. DETAILED DESCRIPTION

[0015] As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent otherwise.

[0016] Unless otherwise indicated, all ranges or ratios disclosed herein should be understood to include any and all values, subranges or subratios contained therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all values ​​therebetween (such as 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10), as well as subranges between a minimum value of 1 and a maximum value of 10 (and including the end values); that is, all subranges or subratios starting with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as (but not limited to) 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0017] Unless otherwise indicated, as used herein, left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as, but not limited to, right-to-left orientation. For non-limiting illustration purposes, left-to-right representation of a divalent linking group or the equivalent -C(O)O- including its representation from right to left or the equivalent -O(O)C- or -OC(O)-.

[0018] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about".

[0019] As used herein, molecular weight values ​​of polymers, such as weight average molecular weight (Mw) and number average molecular weight (Mn), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.

[0020] As used herein, the polydispersity index (PDI) value represents the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (ie, Mw / Mn) of a polymer.

[0021] As used herein, the term "polymer" means homopolymers (eg, prepared from a single monomer species), copolymers (eg, prepared from at least two monomer species), and grafted polymers.

[0022] As used herein, the term "(meth)acrylate" and similar terms, such as "(meth)acrylic acid ester", means methacrylate and / or acrylate. As used herein, the term "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0023] As used herein, the term "electrochromic" and similar terms, such as "electrochromic compound" means having an absorption spectrum that changes in response to an applied potential for at least visible radiation. In addition, as used herein, the term "electrochromic material" means any substance adapted to exhibit electrochromic properties (such as, adapted to have an absorption spectrum that changes in response to an applied potential for at least visible radiation) and includes at least one electrochromic compound.

[0024] As used herein, the term "electric potential" and related terms, such as "electrical potential," means an electrical potential that is capable of causing a response in a material, such as, but not limited to, the conversion of an electrochromic material from one form or state to another, as will be discussed in further detail herein.

[0025] As used herein to modify the term "state", the terms "first" and "second" are not intended to refer to any particular order or timing, but to two different conditions or characteristics. For non-limiting purposes, electrochromic compounds, such as the first state and the second state of an anodizing electrochromic compound may differ in at least one optical property, such as, but not limited to, the absorption of visible light and / or UV radiation. Therefore, according to various non-limiting embodiments disclosed herein, the anodizing electrochromic compound of the present invention may have different absorption spectra in each of the first and second states. For example, but not limiting herein, an anodizing electrochromic compound may be transparent in the first state and have a color in the second state. Alternatively, an anodizing electrochromic compound may have a first color in the first state and a second color in the second state.

[0026] As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs or diagrams. Non-limiting examples of display components include screens, monitors, and security components, such as security indicia.

[0027] As used herein, the term "window" means an aperture adapted to allow radiation to be transmitted therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, baffles, and optical switches.

[0028] As used herein, the term "specular" means a surface that specularly reflects a majority of incident light.

[0029] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below" and the like, are applied to the present invention in the manner as it is depicted in the accompanying drawings. However, it should be understood that the present invention can assume various alternative orientations and therefore, such terms should not be considered limiting.

[0030] As used herein, the terms "formed over", "deposited over", "provided over", "applied over", "positioned over", or "disposed over" mean formed, deposited, provided, applied, positioned, or disposed on an underlying component or a surface of an underlying component, but not necessarily in direct (or adjacent) contact with the underlying component or the surface of the underlying component. For example, "a layer disposed over a substrate" does not exclude the presence of one or more other layers, coatings, or films of the same or different composition between the disposed or formed layer and the substrate.

[0031] As used herein, the terms "interposed" and "interposed between" mean located or disposed between, but not necessarily in direct (or adjacent) contact with the upper and / or lower components or surfaces thereof. For example, "a layer interposed between a first substrate and a second substrate" does not exclude the presence of one or more other layers, coatings or films of the same or different composition located between the interposed layer and the first substrate and / or the second substrate.

[0032] All documents referred to herein, such as but not limited to issued patents and patent applications, are deemed to be "incorporated by reference in their entirety" unless otherwise indicated.

[0033] As used herein, the description of a "straight or branched" group, such as a straight or branched alkyl group, is understood herein to include: methylene or methyl; straight chain groups, such as a straight chain C2-C 20 Alkyl; and suitable branched groups, such as branched C3-C 20 alkyl.

[0034] As used herein, the term "alkyl" refers to a linear or branched, cyclic or non-cyclic C1-C 25 Alkyl. A straight chain or branched chain alkyl may include C1-C 25 Alkyl groups, such as C1-C 20 Alkyl groups, such as C2-C 10 Alkyl groups, such as C1-C 12 Alkyl groups such as C1-C6 alkyl groups. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected include, but are not limited to, the alkyl groups further described herein. Alkyl groups may include "cycloalkyl groups". As used herein, the term "cycloalkyl group" means a suitable cyclic group such as, but not limited to, C3-C6 alkyl groups. 12 Cycloalkyl (including but not limited to cyclic C3-C 10 alkyl, or cyclic C5-C7 alkyl). Examples of cycloalkyl include, but are not limited to, the cycloalkyl groups further described herein. As used herein, the term "cycloalkyl" also includes: bridged ring polycyclic alkyl (or bridged ring polycyclic alkyl), such as, but not limited to, bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and fused ring polycyclic alkyl (or fused ring polycyclic alkyl), such as, but not limited to, octahydro-1H-indenyl and decahydronaphthyl.

[0035] As used herein, the term "heterocycloalkyl" means a group that is appropriately cyclic and has at least one heteroatom (such as, but not limited to, O, S, N, P, and combinations thereof) in the cyclic ring, such as, but not limited to, C2-C 12 Heterocycloalkyl, such as C2-C 10Heterocycloalkyl, such as C5-C7 heterocycloalkyl. Examples of heterocycloalkyl include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyrenyl, and piperidinyl. As used herein, the term "heterocycloalkyl" also includes: bridged ring polycyclic heterocycloalkyl, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclic heterocycloalkyl, such as, but not limited to, octahydrocyclopenta[b]pyrenyl and octahydro-1H-isochromenyl.

[0036] The descriptions, classes, and examples provided herein for alkyl, cycloalkyl, heterocycloalkyl, haloalkyl, and the like also apply to alkane groups, cycloalkane groups, heterocycloalkyl groups, haloalkyl groups, and the like, such as, but not limited to, multivalent alkane groups, such as multivalent alkane linking groups, such as divalent alkane linking groups.

[0037] As used herein, the term "aryl" and related terms, such as "aryl group" means an aromatic cyclic monovalent hydrocarbon radical. As used herein, the term "aromatic" and related terms, such as "aromatic group" means a cyclic conjugated hydrocarbon having a stability significantly greater than that of a hypothetical localized structure (due to the delocalization of π electrons). Examples of aryl groups include C6-C 14 Aryl groups such as, but not limited to, phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0038] As used herein, the term "heteroaryl" includes, but is not limited to, C3-C 18 Heteroaryl, such as (but not limited to) C3-C 10 Heteroaryl (including fused-ring polycyclic heteroaryl) means an aryl group having at least one heteroatom in an aromatic ring or in at least one aromatic ring in the case of a fused-ring polycyclic heteroaryl. Examples of heteroaryl groups include, but are not limited to, furanyl, pyrenyl, pyridyl, quinolyl, isoquinolyl, and pyrimidinyl.

[0039] Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0040] As used herein, the term "nitrogen-containing heterocycle", such as "nitrogen-containing heterocyclic group" or "nitrogen-containing heterocyclic substituent", includes, but is not limited to, nitrogen-containing rings wherein the nitrogen-containing ring is bonded via the ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amines (or cycloaliphatic amines), such as morpholinyl, piperidinyl, pyrrolidinyl, and decahydroisoquinolinyl; and heteroaromatic compounds, such as imidazole, pyrrole, indole, and carbazole.

[0041] As used herein, recitation of a "substituted" group means a group in which at least one hydrogen has been replaced or substituted by a group or "substituent" other than hydrogen, including but not limited to alkyl, cycloalkyl, heterocycloalkyl, aryl and / or heteroaryl groups, such as but not limited to: alkoxy; halide (e.g., F, Cl, I and Br); hydroxy; thiol; alkylthio; arylthio; keto; aldehyde; carboxylate; carboxylic acid; phosphate; phosphate; sulfonic acid; sulfonate; nitro; cyano; alkyl; alkenyl; alkynyl; haloalkyl; perhaloalkyl; heterocycloalkyl; aryl (including alkaryl, including hydroxy substituted aryl such as phenol, and including poly-fused ring aryl); aralkyl; heteroaryl (including poly-fused ring heteroaryl); amine such as -N(R 11 ')(R 12 '), where R 11 ' and R 12 'Each is independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl or heteroaryl; carboxylate; siloxane; alkoxysilane; polysiloxane; amide; carbamate; carbonate; urea; trialkylsilane; nitrogen-containing heterocycle; or a combination thereof, including the classes and examples further described herein. According to some embodiments of the present invention, the substituents of the substituted groups are more specifically described.

[0042] As used herein, the term "halo" and related terms such as "halo group," "halo substituent," "halogen group," and "halogen substituent" refer to a single bonded halogen group such as -F, -Cl, -Br, and -I.

[0043] As used herein, the recitation of "halo-substituted" and related terms (such as, but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and haloheteroaryl) means a group in which at least one and up to (and including) all available hydrogen groups are substituted with halo (such as, but not limited to, F, Cl, or Br). The term "halo-substituted" includes "perhalo-substituted". As used herein, the term perhalo-substituted group and related terms (such as, but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl, or perhaloheteroaryl) means a group in which all available hydrogen groups are substituted with halo. For the purpose of non-limiting illustration: a perhalomethyl group is -CX3; and a perhalophenyl group is -C6X5, where X represents one or more halo groups, such as, but not limited to, F, Cl, Br, or I.

[0044] As used herein, "at least one of" is synonymous with "one or more of," whether elements are listed collectively or individually. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0045] As used herein, "selected from" is synonymous with "selected from", whether the elements are listed collectively or individually. In addition, the phrases "selected from A, B, and C" and "selected from A, B, or C" each mean any one of A, B, or C, or any combination of any two or more of A, B, or C. For example, A alone; or B alone; or C alone; or A and B; or A and C; or B and C; or all of A, B, and C.

[0046] The discussion of the invention herein may describe certain features as "specific" or "preferred" within certain limitations (e.g., "preferred," "more preferred," or "even more preferred" within certain limitations). It is to be understood that the invention is not limited to or by such specific or preferred limitations, but rather encompasses the full scope of the disclosure.

[0047] As used herein and according to some embodiments, the term "ketone", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "ketone group" and "ketone substituent" include species represented by -C(O)R, wherein R is selected from groups other than hydrogen as described below.

[0048] As used herein and according to some embodiments, the term "carboxylic acid", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "carboxylic acid group" and "carboxylic acid substituent" include species represented by -C(O)OH.

[0049] As used herein and according to some embodiments, the term "ester", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms, such as "ester group" and "ester substituent" means a carboxylate group represented by -C(O)OR, wherein R is selected from groups other than hydrogen as described below.

[0050] As used herein and according to some embodiments, the term "carboxylate", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "carboxylate group" and "carboxylate substituent" include species represented by -OC(O)R, wherein R is selected from the groups described below.

[0051] As used herein and according to some embodiments, the term "amide", such as with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms such as "amide group" and "amide substituent" include species represented by -C(O)N(R)(R) or -N(R)C(O)R, wherein each R is independently selected from groups described below.

[0052] As used herein and according to some embodiments, the term "carbonate", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "carbonate group" and "carbonate substituent" include substances represented by -OC(O)OR, wherein R is selected from groups other than hydrogen as described below.

[0053] As used herein and according to some embodiments, the term "carbamate", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "carbamate" and "carbamate substituent" include species represented by -OC(O)N(R)(H) or -N(H)C(O)OR, wherein R at each occurrence is independently selected from groups other than hydrogen as described below.

[0054] As used herein and according to some embodiments, the term "urea", such as with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms such as "urea group" and "urea substituent" include species represented by -N(R)C(O)N(R)(R), wherein each R is independently selected from groups described below.

[0055] As used herein and according to some embodiments, the term "silanoxy", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "silanoxy group" and "silanoxy substituent" include species represented by -O-Si(R)3, wherein each R is independently selected from groups other than hydrogen as described below.

[0056] As used herein and according to some embodiments, the term "alkoxysilane", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "alkoxysilane group" and "alkoxysilane substituent" include alkoxysilanes composed of -Si(OR") w (R) t A substance represented by wherein w is 1 to 3 and t is 0 to 2, with the proviso that the sum of w and t is 3; for each w, R" is independently selected from alkyl; and for each t, ​​R is independently selected from groups other than hydrogen as described below.

[0057] As used herein and according to some embodiments, the term "polysiloxane", such as groups and substituents of various groups with respect to the compounds and components of the present invention, and related terms such as "polysiloxane group" and "polysiloxane substituent" include substances represented by the following formula (A):

[0058] Regarding formula (A): t' is greater than or equal to 2, such as 2 to 200; for each t', R f and R g are each independently selected from the group R described below except hydrogen; and R h is independently a group R as described below.

[0059] Unless otherwise indicated, each R group for each of the foregoing ketones, esters (esters of carboxylic acids), carboxylates, amides, carbonates, urethanes, ureas, siloxanes, alkoxysilane groups, and polysiloxane groups is independently selected at each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof (including classes and examples thereof as previously described herein).

[0060] In some embodiments, the counterions (such as countercations and / or counteranions) of a component referred to herein refer to the counterions of the component when the component is prepared separately from the electrochromic layer and / or electrochromic composition of the present invention and / or before being combined with the electrochromic layer and / or electrochromic composition of the present invention.

[0061] According to the present invention, the electrochromic material (of the electrochromic layer of the electrochromic device) includes an anode component, wherein the anode component includes an anode component anion selected from at least one anode component anion represented by formula (I) or formula (II) as provided above. The anode component anion can be described as including an anode portion (group or part), such as (10H-phenothiazine-10-base) part, and an anion covalently bonded to the anode portion, such as a sulfonate anion or a trifluoromethanesulfonamide anion. In some other embodiments, the anion of the anode component anion is covalently bonded to the anode group or part by a divalent straight or branched alkane linking group. In some other embodiments, the anode component anion is an anode coloring electrochromic compound or a group with an anion covalently bonded thereto.

[0062] According to some embodiments of the present invention and with reference to the anode component anion represented by formula (I), R 1 Selected from divalent straight or branched C1-C 10 Alkane linking group.

[0063] In some embodiments and with reference to the anode component anion represented by formula (II), R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0064] With reference to the anode component anion represented by formula (I) and according to some embodiments, R 1 is selected from divalent straight or branched C1-C5 alkyl groups. 1 Selected from divalent methane, divalent ethane, divalent straight-chain or branched-chain propane, divalent straight-chain or branched-chain butane and divalent straight-chain or branched-chain pentane.

[0065] With reference to the anode component anion represented by formula (II) and according to some embodiments, R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 is selected from a linear or branched C1-C5 perfluorinated alkyl group. 2 is selected from divalent methane, divalent ethane, divalent linear or branched propane, divalent linear or branched butane, and divalent linear or branched pentane. In some other embodiments, R 3 Selected from fluorinated or perfluorinated versions or derivatives of methyl, ethyl, linear or branched propyl, linear or branched butyl and linear or branched pentyl.

[0066] In some embodiments of the invention, anode component anions (having anions covalently bonded thereto), such as represented by Formula (I) and Formula (II), may be prepared according to the non-limiting synthetic illustrations provided further in the Examples herein.

[0067] According to some other embodiments, the anode component including the anode component anion further includes a counter cation. The types and examples of cations from which each counter cation can be independently selected include, but are not limited to: alkali metal cations, such as lithium cations (Li + ), sodium cation (Na + ) and potassium cation (K + ); alkaline earth metal cations such as Mg 2+ , Ca 2+ And Ba 2+ ; optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cations, such as optionally substituted N,N-disubstituted pyrrolidinium cations, optionally substituted N,N-disubstituted piperidinium cations, and optionally substituted N,N-disubstituted morpholinium cations; optionally substituted nitrogen-containing aromatic heterocyclic ammonium cations, such as optionally substituted N-substituted pyridinium cations, optionally substituted N-substituted quinolinium cations, and optionally substituted N-substituted isoquinolinium cations; and tetrasubstituted ammonium cations described in further detail below. The optional substituents of the classes and examples of the ammonium cations can be selected from the classes and examples of substituents previously described herein, such as (but not limited to) straight or branched alkyl, cycloalkyl, and aryl. The N-substituted and N,N-disubstituted groups of the ammonium cations can be selected from the classes and examples of substituents previously described herein, such as (but not limited to) straight or branched alkyl, cycloalkyl, and aryl.

[0068] In some embodiments, the counter cation of the anode component is a monocation. According to some other embodiments, the counter cation of the anode component is selected from tetrasubstituted ammonium cations represented by the following formula (B), Formula (B)

[0069] Regarding formula (B), R a , R b , R c and R d Each is independently selected from a linear or branched alkyl group, an unsubstituted cycloalkyl group, a substituted cycloalkyl group, an unsubstituted aryl group and a substituted aryl group. a , R b , R c and R d Each independently selected from a linear or branched C1-C 10In some embodiments, the present invention relates to a cycloalkyl group, ...

[0070] In some embodiments and with respect to Formula (B), R a , R b , R c and R d In some other embodiments, R of formula (B) is independently selected from a linear or branched alkyl group. a , R b , R c and R d Each of which is independently selected from a linear or branched C1-C 10 alkyl.

[0071] In some embodiments, each counter cation of the anode component is independently selected from tetra(straight or branched alkyl)ammonium cations. In some other embodiments, each counter cation of the anode component is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0072] In some embodiments, the anode component consists of or consists of: an anode component anion selected from at least one anode component anion represented by formula (I) or formula (II); and a counter cation, wherein the anode component has an equal number of anions and counter cations and correspondingly has a neutral charge.

[0073] In some embodiments, the anode component anion is present in the electrochromic layer in an amount of 0.25 weight percent to 6.25 weight percent, or 0.5 weight percent to 5 weight percent, or 1 weight percent to 3 weight percent, in each case the weight percent is based on the total weight of the electrochromic layer.

[0074] According to some embodiments, in addition to the anode component anion having a covalently bonded anion (such as represented by formula (I) and / or formula (II)), the anode component of the electrochromic layer also includes one or more other anode electrochromic compounds, such as (but not limited to): ferrocene and / or ferrocene derivatives (wherein at least one cyclopentadienyl ring thereof is substituted with at least one substituent (including the substituents previously described herein)); 5,10-dihydro-5,10-di(straight or branched C1-C 10alkyl) phenazines, such as 5,10-dihydro-5,10-dimethylphenazine; N-substituted phenoxazines, such as N-phenylphenoxazine; and combinations thereof. In some embodiments, the other anode electrochromic components are present in an amount of 1 weight percent to 50 weight percent, 1 weight percent to 25 weight percent, or 1 weight percent to 10 weight percent, or 1 weight percent to 5 weight percent, each weight percent being based on the total weight of the anode component anion and the other anode electrochromic components. According to some embodiments, when another anode component is present (in addition to the anode component anion having a covalently bonded anion), another cathode component (or other suitable amount of cathode component) may also be present. In some embodiments, the other cathode components include one or more cathode components represented by formula (III) and / or (IV).

[0075] In some embodiments, the cathode component of the electrochromic layer of the electrochromic device includes at least one of the following: a 1,1'-disubstituted 4,4'-bipyridinium cation represented by the following formula (III), or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted 4,4'-bipyridinium) cation represented by the following formula (VI): Formula (III) Formula (IV)

[0076] Regarding formula (III), R 4 and R 5 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl.

[0077] With respect to formula (IV) and according to some embodiments, R 6 and R 8 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and R 7 Selected from divalent straight or branched C1-C 10 Alkane linking group.

[0078] R of formula (III) can be selected independently from 4 and R 5 and R of formula (IV) 6 and R 8The aryl groups in the unsubstituted aryl and substituted aryl groups include aryl groups as previously described herein, such as (but not limited to) phenyl, naphthyl, phenanthrenyl and anthracenyl. R of formula (III) can be selected independently from 4 and R 5 and R of formula (IV) 6 and R 8 The cycloalkyl groups in the unsubstituted cycloalkyl and substituted cycloalkyl groups include cycloalkyl groups as previously described herein, such as, but not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0079] R of formula (III) can be selected independently from 4 and R 5 and R of formula (IV) 6 and R 8 The substituents in the substituted cycloalkyl and substituted aryl groups include the substituents previously described herein. In some embodiments, R of formula (III) can be selected from each of which is independently selected from 4 and R 5 and R of formula (IV) 6 and R 8 Each substituent in the substituted cycloalkyl and substituted aryl is independently selected from: alkoxy; halide (e.g., F, Cl, I and Br); hydroxy; thiol; alkylthio; arylthio; keto; aldehyde; haloalkyl; perhaloalkyl; heterocycloalkyl; aryl; aralkyl (such as benzyl); heteroaryl; and amine.

[0080] R of formula (III) can be selected independently from 4 and R 5 and R of formula (IV) 6 and R 8 The straight chain or branched chain alkyl group includes the types and examples of alkyl groups previously described herein, such as (but not limited to) methyl, ethyl, straight chain or branched chain propyl, straight chain or branched chain butyl, straight chain or branched chain pentyl, straight chain or branched chain hexyl, and straight chain or branched chain heptyl.

[0081] Further with respect to formula (III) and according to some embodiments of the present invention, R 4 and R 5 Each is independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group.

[0082] Further with respect to formula (IV) and according to some embodiments of the present invention, R 6 and R 8 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and R 7is selected from a divalent straight or branched C1-C8 alkane linking group. In some other embodiments, R of formula (IV) 7 A divalent straight chain or branched C1-C5 alkane linking group, such as a divalent straight chain or branched C3-C5 alkane linking group.

[0083] According to some embodiments of the present invention, the cathode component further includes a counter anion. In some other embodiments, the cathode component includes an equal number of cations and counter anions (or anions) and accordingly, the cathode component has a net neutral charge. In some embodiments, each counter anion of the cathode component is independently selected from: BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C - or B(phenyl)4 - In some embodiments, the counter anions of the cathode component do not include and are not selected from anions of the anode component such as those represented by formula (I) and (II).

[0084] According to some embodiments of the invention, the cathode component is present in the electrochromic layer in an amount of 0.25 weight percent to 6.25 weight percent, or 0.5 weight percent to 5 weight percent, or 1 weight percent to 3 weight percent, in each case, the weight percent is based on the total weight of the electrochromic layer.

[0085] In some embodiments of the present invention, the electrochromic layer of the electrochromic device of the present invention includes an electrolyte. In some embodiments, the electrolyte includes at least one electrolyte anion and at least one electrolyte cation. In some embodiments, the electrolyte of the electrochromic layer includes an equal number of electrolyte anions and electrolyte cations, and has a net neutral charge accordingly.

[0086] In some embodiments, the electrolyte of the electrochromic layer includes at least one electrolyte anion, wherein each electrolyte anion is independently selected from chloride, hexafluorophosphate, and bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide. In some other embodiments, the electrolyte of the electrochromic layer includes at least one electrolyte cation, wherein each electrolyte cation is independently selected from: sodium; potassium; lithium; ammonium cations, such as tetra(linear or branched C1-C6 alkyl)ammonium, and tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl)- 6 alkyl)ammonium; 1-(straight chain or branched C1-C6 alkyl)-3-(straight chain or branched C1-C6 alkyl)imidazolium; 1-(straight chain or branched C1-C6 alkyl)-1-(straight chain or branched C1-C6 alkyl)pyrrolidinium; 1-(straight chain or branched C1-C6 alkyl)-1-(straight chain or branched C1-C6 alkyl)piperidinium; or a phosphonium cation, such as (but not limited to) tetra(straight chain or branched C1-C6 alkyl)phosphonium, or tri(C5-C8 cycloalkyl)-(straight chain or branched C1-C6 alkyl)phosphonium.

[0087] In some embodiments, the electrolyte of the electrochromic layer includes: at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(straight or branched C1-C6 alkylsulfonyl)imide; and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(straight or branched C1-C6 alkyl)-3-(straight or branched C1-C6 alkyl)imidazolium, 1-(straight or branched C1-C6 alkyl)-1-(straight or branched C1-C6 alkyl)pyrrolidinium, or 1-(straight or branched C1-C6 alkyl)-1-(straight or branched C1-C6 alkyl)piperidinium.

[0088] In some other embodiments, the electrolyte of the electrochromic layer includes: at least one electrolyte anion, wherein each electrolyte anion is bis(trifluoromethylsulfonyl)imide; and at least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-1-butylpyrrolidinium and 1-methyl-1-propylpiperidinium.

[0089] In some embodiments, the electrolyte is present in the electrochromic layer in an amount of 1 weight percent to 75 weight percent, or 5 weight percent to 50 weight percent, or 10 weight percent to 30 weight percent, in each case the weight percent is based on the total weight of the electrochromic layer.

[0090] According to some other embodiments, the electrochromic layer of the present invention includes a solvent. In some other embodiments, the solvent replaces the electrolyte or is present in the electrochromic layer together with it. In some embodiments, the solvent may include at least one of the following: ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, cyclopentane, α, ω-(C2-C8) dinitrile or di(straight or branched C1-C8) acetamide. It is not intended to be bound by any theory and according to some embodiments, it is believed that the solvent at least partially acts as a plasticizer (or plasticizes the electrochromic layer) in the electrochromic layer. In some embodiments, the solvent is present in the electrochromic layer in an amount of 10 to 75 weight percent, or 20 to 60 weight percent, in each case, the weight percent is based on the total weight of the electrochromic layer and the solvent.

[0091] The electrochromic layer of the electrochromic device of the present invention comprises a polymer matrix. The polymer matrix comprises at least one polymer. In some embodiments, the polymer matrix is ​​a gelled polymer matrix, a cross-linked polymer matrix and / or a thermoplastic polymer matrix.

[0092] In some embodiments, the polymer matrix includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)), or poly((linear or branched C1-C8 alkyl)(meth)acrylate).

[0093] In some embodiments, the polymer matrix is ​​present in the electrochromic layer in an amount of 5 weight percent to 80 weight percent, or 10 weight percent to 60 weight percent, or 15 weight percent to 50 weight percent, in each case the weight percent is based on the total weight of the electrochromic layer.

[0094] In some embodiments, the electrochromic layer of the electrochromic device of the present invention may further include one or more optional additives recognized in the prior art, such as (but not limited to) thermal stabilizers, UV stabilizers, rheological modifiers, static colorants (such as static colorants and / or static dyes), kinetic additives (accelerating electrode reactions) and combinations thereof. A non-limiting class of thermal stabilizers recognized in the prior art is phenols, such as 2,6-di-tert-butylphenol and compounds including 2,6-di-tert-butylphenol groups or moieties. A non-limiting class of UV stabilizers recognized in the prior art is hindered amine light stabilizers (HALS), such as 2,2,6,6-tetramethylpiperidine and compounds including 2,2,6,6-tetramethylpiperidine groups or moieties. Static colorants include colorants whose absorption spectra do not change in response to actinic radiation (such as UV and / or visible light) or applied potentials, and do not include photochromic compounds and electrochromic compounds. Non-limiting classes of kinetic additives include salts such as alkali and alkaline earth metal salts of perchlorates, tetrafluoroborates, and hexafluorophosphates; and tetraalkylammonium salts. Non-limiting examples of rheological modifiers include dialkoxyacetophenones such as 3',4'-dimethoxyacetophenone; and optionally substituted cycloalkylaryl ketones such as 1-hydroxycyclohexyl phenyl ketone. Each optional additive may be present in any suitable active amount, such as 0.05 weight percent to 5 weight percent, based on the total solid weight of the electrochromic layer (including the weight of the optional additives).

[0095] The electrochromic layer of the electrochromic device of the present invention can have any suitable thickness. In some embodiments, the electrochromic layer has a thickness of 50 microns to 800 microns.

[0096] For non-limiting illustrative purposes, an electrochromic device (3) according to the present invention is depicted in Figure 1 The electrochromic device (3) includes a first substrate (11) having a first surface (14) and a second surface (17). The first surface (14) of the first substrate (11) includes a conductive first transparent electrode layer (20). The first transparent electrode layer (20) is located above at least a portion of the first surface (14) of the first substrate (11). In some embodiments, the first transparent electrode layer (20) is in the form of one or more patterns (such as one or more designs and / or logos) above the first surface (14) of the first substrate (11). In some other embodiments, the first transparent electrode layer (20) forms a substantially continuous layer above the first surface (14) of the first substrate (11). In some embodiments, the first transparent electrode layer (20) is in electrical contact with at least one first electrical conductor (21), which may be a first conductive wire.

[0097] The electrochromic device (3) includes a second substrate (23) having a first surface (26) and a second surface (29). The first surface (26) of the second substrate (23) includes a conductive second transparent electrode layer (32). The second transparent electrode layer (32) is located above at least a portion of the first surface (26) of the second substrate (23). In some embodiments, the second transparent electrode layer (32) is in the form of one or more patterns (such as one or more designs and / or logos) above the first surface (26) of the second substrate (23). In some other embodiments, the second transparent electrode layer (32) forms a substantially continuous layer above the first surface (26) of the second substrate (23). In some embodiments, the second transparent electrode layer (32) is in electrical contact with at least one second electrical conductor (33), which may be a second conductive second wire.

[0098] Further references Figure 1 In the electrochromic device (3), the first transparent electrode layer (20) and the second transparent electrode layer (32) are spaced apart from each other and face each other.

[0099] The electrochromic device (3) further comprises an electrochromic layer (35) interposed between the first transparent electrode layer (20) and the second transparent electrode layer (32). In some embodiments, the electrochromic layer (35) is interposed between the first transparent electrode layer (20) and the second transparent electrode layer (32) and is in a contiguous relationship with the first transparent electrode layer and the second transparent electrode layer.

[0100] In some embodiments, the first substrate and the second substrate of the electrochromic device of the present invention are each independently selected from a transparent substrate. In some embodiments, the transparent substrate from which the first substrate and the second substrate are each independently selected is made of materials including, but not limited to, silica glass, organic polymers (such as, but not limited to, polycarbonate polymers) and combinations thereof. In some embodiments, the transparent substrate from which the first substrate and the second substrate are each independently selected is made of a material including silica glass. The first substrate and the second substrate may each independently have any suitable thickness. In some embodiments, the first substrate and the second substrate each independently have a thickness of 1 mm to 25 mm, or 2 mm to 10 mm.

[0101] In some embodiments, the first and second transparent electrode layers of the electrochromic device of the present invention include conductive inorganic oxides, conductive organic materials, conductive metals and / or conductive carbon, such as carbon nanotubes and / or graphene. Examples of conductive inorganic oxides include, but are not limited to: tin oxide, which may be doped with a doping material such as indium; and zinc oxide, which may further include, for example, aluminum. Examples of conductive organic materials include, but are not limited to, poly(3,4-ethylenedioxythiophene), poly(4,4-dioctylcyclopentadithiophene) and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate). In some embodiments, the first and second transparent electrode layers may each independently be in the form of a metal wire mesh, a carbon nanotube mesh and / or a graphene layer. In some embodiments, the first and second transparent electrode layers are each independently selected from a semi-transparent metal layer. In some other embodiments, one of the first and second transparent electrode layers includes (or has associated therewith) a reflective metal layer (including, for example, aluminum, gold and / or silver), and the electrochromic device is a reflective electrochromic device, such as a controllable reflective mirror.

[0102] According to some embodiments, the first and second electrode layers of the electrochromic device of the present invention each independently include a conductive material selected from the group consisting of indium tin oxide, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), or a combination thereof.

[0103] According to some embodiments of the present invention, the first and second electrode layers of the electrochromic device can each independently have any suitable thickness, provided that they are both transparent and conductive. In some embodiments, the first and second electrode layers of the electrochromic device of the present invention each independently have a thickness of 0.01 micrometers to 10 micrometers.

[0104] Examples of articles that may include or be defined by the electrochromic devices of the present invention, such as articles, include (but are not limited to): energy-saving and / or privacy transparencies (or windows), such as architectural and transportation transparencies or windows; mirrors, such as rearview mirrors; filters; and ophthalmic articles, such as corrective lenses, non-corrective lenses, magnifying glasses, protective lenses and goggles; and any other articles or applications requiring variable and controllable light transmission and / or color.

[0105] The present invention also relates to an electrochromic composition comprising: (i) a cathode component; (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by formula (I) or formula (II) as previously described herein; (iii) an optional electrolyte; (iv) a polymeric thickener; and (v) a solvent.

[0106] The cathode component, the anode component including an anode component anion selected from at least one anode component anion represented by formula (I) or formula (II), and the optional electrolyte are each as previously described herein with respect to the electrochromic layer of the electrochromic device of the present invention.

[0107] In some embodiments, the cathode component is present in the electrochromic composition in an amount from 0.25 weight percent to 6.25 weight percent, or from 0.5 weight percent to 5 weight percent, or from 1 weight percent to 3 weight percent, in each case, the weight percent is based on the total weight of the electrochromic composition.

[0108] In some embodiments, the anode component anion is present in the electrochromic composition in an amount of 0.25 weight percent to 6.25 weight percent, or 0.5 weight percent to 5 weight percent, or 1 weight percent to 3 weight percent, in each case, the weight percent is based on the total weight of the electrochromic composition.

[0109] According to some embodiments, in addition to the anode component anion having a covalently bonded anion (such as represented by Formula (I) and / or Formula (II)), the anode component of the electrochromic composition includes one or more other anode electrochromic compounds, such as (but not limited to): ferrocene and / or ferrocene derivatives (wherein at least one cyclopentadienyl ring thereof is substituted with at least one substituent (including the substituents previously described herein)); 5,10-dihydro-5,10-di(straight or branched C1-C 10 alkyl) phenazines, such as 5,10-dihydro-5,10-dimethylphenazine; N-substituted phenoxazines, such as N-phenylphenoxazine; and combinations thereof. In some embodiments, the other anode electrochromic components are present in an amount of 1 weight percent to 50 weight percent, 1 weight percent to 25 weight percent, or 1 weight percent to 10 weight percent, or 1 weight percent to 5 weight percent, each weight percent being based on the total weight of the anode component anion and the other anode electrochromic components. According to some embodiments, when another anode component is present (other than the anode component anion having a covalently bonded anion), another cathode component (or other suitable amount of cathode component) may also be present. In some embodiments, the other cathode components include one or more cathode components represented by formula (III) and / or (IV).

[0110] In some embodiments, the electrolyte is present in the electrochromic composition in an amount of 1 weight percent to 75 weight percent, or 5 weight percent to 50 weight percent, or 10 weight percent to 30 weight percent, in each case, the weight percent is based on the total weight of the electrochromic composition.

[0111] In some embodiments, the polymeric thickener of the electrochromic composition of the electrochromic composition includes a polymer, wherein the polymer includes at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(straight or branched C1-C6 alkylene)), or poly((straight or branched C1-C8 alkyl)(meth)acrylate).

[0112] In some embodiments, the polymeric thickener is present in the electrochromic composition in an amount of 5 weight percent to 80 weight percent, or 10 weight percent to 60 weight percent, or 15 weight percent to 50 weight percent, in each case, the weight percent is based on the total weight of the electrochromic composition.

[0113] The electrochromic composition of the present invention includes a solvent. In some embodiments, the solvent of the electrochromic composition includes at least one of the following: ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, cyclopentane, α,ω-(C2-C8) dinitrile or di(linear or branched C1-C8) acetamide.

[0114] In some embodiments, the solvent is present in the electrochromic composition in an amount of 10 to 75 weight percent, or 20 to 60 weight percent, or 25 to 50 weight percent, in each case the weight percent is based on the total weight of the electrochromic composition.

[0115] According to some embodiments, the anode component including the anode component anion further includes a counter cation. The categories and examples of cations from which each counter cation can be independently selected include the categories and examples described previously herein for electrochromic devices. In some embodiments of the electrochromic compositions of the present invention, each counter cation is independently selected from tetra(straight or branched alkyl)ammonium cations. According to some other embodiments, each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0116] In some embodiments, the cathode component of the electrochromic composition further comprises a counter anion, wherein each counter anion of the cathode component is selected from BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C - and B(phenyl)4 -In some embodiments, the counter anions of the cathode component of the electrochromic composition do not include and are not selected from anions of the anode component such as those represented by formula (I) and (II).

[0117] In some embodiments, the electrochromic composition of the present invention may include one or more optional additives recognized in the prior art, such as (but not limited to) thermal stabilizers, UV stabilizers, rheological modifiers, static colorants (such as static colorants and / or static dyes), kinetic additives (to accelerate electrode reactions), and combinations thereof. In various cases, the optional additives are as previously described herein with respect to the electrochromic device of the present invention. Based on the total weight of the electrochromic composition (including the weight of the optional additives), each optional additive may be present in the electrochromic composition in any suitable active amount, such as 0.05 weight percent to 5 weight percent.

[0118] According to some embodiments of the present invention, the electrochromic layer of the electrochromic device is formed by the electrochromic composition of the present invention. According to some embodiments of the present invention, the formation of the electrochromic composition and the electrochromic layer includes the following steps. First, all components of the electrochromic composition except the polymeric thickener are mixed under shear (such as using an impeller) until a uniform mixture is formed. Then, the polymeric thickener is added and the combination is homogenized to cause the formation of a viscous slurry. A liquid film of a viscous slurry is formed on a sacrificial or temporary liner (in some embodiments, composed of polyethylene terephthalate), such as using a scraper or a stretching rod. The liquid film is subjected to high temperatures (such as 60° C. to 90° C.) for 3 to 10 minutes when it is located on a sacrificial / temporary liner, causing the formation of a cured film / layer, which is an electrochromic layer. The cured film / electrochromic layer is separated from the sacrificial / temporary liner (which is discarded), cut to a size (as needed) and placed above or on the first transparent electrode layer of the first substrate. The second transparent electrode of the second substrate is placed above or on the other (or opposite / exposed) side of the electrochromic layer to form a stack comprising the first substrate, the first transparent electrode, the electrochromic layer, the second transparent electrode and the second substrate. The stack may further include an electrical connector that is independently electrically contacted with the first and second transparent electrodes. The stack (with an optional gasket around the outer edge of at least the electrochromic layer) is subjected to vacuum lamination while applying a high temperature, such as 110°C to 200°C, for a period of time such as 10 to 30 minutes. After cooling, the electrochromic device thus formed is removed from the vacuum lamination device.

[0119] According to the present invention, there is also provided a compound represented by formula (IIa) as previously described herein. 2 Divalent linking group and R 3 The groups are each as described herein before in relation to formula (II) of the electrochromic device of the present invention.

[0120] In some embodiments, R of Formula (IIa) 2 Selected from divalent straight or branched C1-C 10 An alkane linking group; and R of formula (IIa) 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0121] In some other embodiments, R of Formula (IIa) 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R of formula (IIa) 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0122] In some embodiments, the compound represented by formula (IIa) can be prepared by making a salt of an anion represented by formula (II), such as sodium (Na + ) or potassium (K + ) salts with strong acids such as, but not limited to, HCl, sulfuric acid (H2SO4) and bistriflimidic acid, followed by art-recognized purification, separation and work-up procedures.

[0123] According to the present invention, there is also provided a salt comprising an anion represented by formula (II) as previously described herein. 2 Divalent linking group and R 3 The groups are each as described herein before in relation to formula (II) of the electrochromic device of the present invention.

[0124] In some embodiments, R in formula (II) of the salt according to the present invention is 2 Selected from divalent straight or branched C1-C 10 Alkane linking group; and R in the formula (II) of the salt of the present invention 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0125] In some other embodiments, R in the formula (II) of the salt of the present invention is 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R in the formula (II) of the salt of the present invention 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0126] According to some embodiments, the salt of the present invention includes: an anion represented by formula (II); and a counter cation. In some embodiments of the salt of the present invention, the number of anions and counter cations is equal, and thus the salt has a neutral charge. In some embodiments, the counter cation of the salt according to the present invention is as previously described herein for the counter cation of the anode component of the present invention, such as, but not limited to, described with respect to formula (B).

[0127] In some embodiments, the counter cation of the salt according to the present invention is selected from tetra(straight or branched alkyl)ammonium cations. In some other embodiments, the counter cation of the salt according to the present invention is selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0128] The salt of the present invention may have any suitable form, such as in solid form or in the form of an ionic liquid. In some embodiments, the salt of the present invention is present in the form of a liquid mixture, which further includes a solvent, such as water and / or an organic solvent. The organic solvent may be selected from any suitable organic solvent, such as, but not limited to, ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, cyclopentane, α, ω-(C2-C8) dinitrile or di(straight or branched C1-C8) acetamide.

[0129] The invention may be further characterized by one or more of the following non-limiting clauses.

[0130] Item 1: An electrochromic device comprising: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer, The first transparent electrode layer and the second transparent electrode layer are spaced apart from each other; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent conductive electrode layer, wherein the electrochromic layer comprises, (i) cathode components, (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by the following formula (I) or formula (II), Wherein for formula (I), R 1 is selected from divalent straight or branched alkane linking groups, and Wherein for formula (II), R 2 is selected from divalent straight or branched alkane linking groups, and R 3is selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl, (iii) optionally an electrolyte, and (iv) Polymer matrix.

[0131] Item 2: An electrochromic device according to Item 1, wherein for Formula (I), R 1 Selected from divalent straight or branched C1-C 10 an alkane linking group, and Wherein for formula (II), R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0132] Item 3: An electrochromic device according to Item 1 or Item 2, wherein for Formula (I), R 1 is selected from divalent straight or branched C1-C5 alkyl groups, and Wherein for formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0133] Clause 4: The electrochromic device of clause 1, wherein the anode component further comprises a counter cation.

[0134] Item 5: An electrochromic device as in Item 4, wherein each counter cation is independently selected from an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation, an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation, a tetrasubstituted ammonium cation, or a combination thereof.

[0135] Clause 6: The electrochromic device of clause 4 or clause 5, wherein each counter cation is independently selected from a tetra-substituted ammonium cation represented by formula (B), Formula (B) Where R a , R b , R c and R d Each is independently selected from a linear or branched alkyl group, an unsubstituted cycloalkyl group, a substituted cycloalkyl group, an unsubstituted aryl group and a substituted aryl group.

[0136] Clause 7: The electrochromic device of clause 6, wherein R a , R b , R c and R dEach independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0137] Clause 8: An electrochromic device according to clause 6 or clause 7, wherein R a , R b , R c and R d Each independently selected from a linear or branched C1-C 10 alkyl.

[0138] Clause 9: An electrochromic device as in any one of clauses 4, 5, 6, 7 or 8, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0139] Item 10: An electrochromic device according to any one of Items 4, 5, 6, 7, 8 or 9, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0140] Item 11: An electrochromic device as described in any of items 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein the cathode component comprises at least one of the following: a 1,1'-disubstituted-4,4'-bipyridinium cation represented by the following formula (III), or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted-4,4'-bipyridinium) cation represented by the following formula (VI), Formula (III) Formula (IV) Wherein for formula (III), R 4 and R 5 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and Wherein for formula (IV), R 6 and R 8 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and R 7 Selected from divalent straight or branched C1-C 10 Alkane linking group.

[0141] Item 12: The electrochromic device of Item 11, wherein for Formula (III), R4 and R 5 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and Wherein for formula (IV), R 6 and R 8 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and R 7 Selected from divalent straight or branched C1-C8 alkane linking groups.

[0142] Item 13: An electrochromic device as in any one of items 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, wherein the cathode component further comprises a counter anion, wherein each counter anion of the cathode component is selected from BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C - or B(phenyl)4 - .

[0143] Clause 14: An electrochromic device as in any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the electrolyte is present and comprises, at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide, and At least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(straight or branched C1-C6 alkyl)-3-(straight or branched C1-C6 alkyl)imidazolium; 1-(straight or branched C1-C6 alkyl)-1-(straight or branched C1-C6 alkyl)piperidinium; or a phosphonium cation, such as (but not limited to) tetra(straight or branched C1-C6 alkyl)phosphonium, or tri(C5-C8 cycloalkyl)-(straight or branched C1-C6 alkyl)phosphonium; or an ammonium cation, such as (but not limited to) tetra(straight or branched C1-C6 alkyl)ammonium, and tri(C5-C8 cycloalkyl)-(straight or branched C1-C6 alkyl)ammonium.

[0144] Item 15: An electrochromic device as described in any of items 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein the polymer matrix comprises a polymer, wherein the polymer comprises at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)) or poly((linear or branched C1-C8 alkyl)(meth)acrylate).

[0145] Item 16: An article comprising the electrochromic device of any of items 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, wherein the article is selected from an energy-saving transparency, a privacy transparency, a mirror, a filter or an ophthalmic article.

[0146] Item 17: An electrochromic composition comprising: (i) cathode components, (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by the following formula (I) or formula (II), Wherein for formula (I), R 1 is selected from divalent straight or branched alkane linking groups, and Wherein for formula (II), R 2 is selected from divalent straight or branched alkane linking groups, and R 3 is selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl, (iii) optionally an electrolyte, (iv) polymeric thickeners; and (v) Solvent.

[0147] Item 18: The electrochromic composition of Item 17, wherein for formula (I), R 1 Selected from divalent straight or branched C1-C 10 an alkane linking group, and Wherein for formula (II), R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0148] Item 19: The electrochromic composition of Item 17 or Item 18, wherein for formula (I), R 1 is selected from divalent straight or branched C1-C5 alkyl groups, and Wherein for formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0149] Item 20: The electrochromic composition of any of Items 17, 18, or 19, wherein the anode component further comprises a counter cation.

[0150] Item 21: The electrochromic composition of Item 20, wherein each counter cation is independently selected from an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation, an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation, a tetrasubstituted ammonium cation, or a combination thereof.

[0151] Item 22: The electrochromic composition of Item 20 or Item 21, wherein each counter cation is selected from a tetrasubstituted ammonium cation represented by the following formula (B), Formula (B) Where R a , R b , R c and R d Each is independently selected from a linear or branched alkyl group, an unsubstituted cycloalkyl group, a substituted cycloalkyl group, an unsubstituted aryl group and a substituted aryl group.

[0152] Item 23: The electrochromic composition of Item 22, wherein R a , R b , R c and R d Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0153] Item 24: An electrochromic composition according to Item 22 or Item 23, wherein R a , R b , R c and R d Each independently selected from a linear or branched C1-C 10 alkyl.

[0154] Item 25: An electrochromic composition as in any one of items 17, 18, 19, 20, 21, 22, 23 or 24, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0155] Item 26: An electrochromic composition according to any one of Items 17, 18, 19, 20, 21, 22, 23, 24 or 25, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0156] Item 27: An electrochromic composition as described in any of Items 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26, wherein the cathode component comprises at least one of the following: a 1,1'-disubstituted-4,4'-bipyridinium cation represented by the following formula (III), or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted-4,4'-bipyridinium) cation represented by the following formula (VI), Formula (III) Formula (IV) Wherein for formula (III), R 4 and R 5 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and Wherein for formula (IV), R 6 and R 8 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and R 7 Selected from divalent straight or branched C1-C 10 Alkane linking group.

[0157] Item 28: The electrochromic composition of Item 27, wherein for formula (III), R 4 and R 5 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and Wherein for formula (IV), R 6 and R 8 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and R 7 Selected from divalent straight or branched C1-C8 alkane linking groups.

[0158] Item 29: An electrochromic composition as in any one of Items 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28, wherein the cathode component further comprises a counter anion, wherein each counter anion of the cathode component is selected from BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C- or B(phenyl)4 - .

[0159] Clause 30: The electrochromic composition of any of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 or 29, wherein the electrolyte is present and comprises, at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide, and At least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(straight or branched C1-C6 alkyl)-3-(straight or branched C1-C6 alkyl)imidazolium; 1-(straight or branched C1-C6 alkyl)-1-(straight or branched C1-C6 alkyl)piperidinium; or a phosphonium cation, such as (but not limited to) tetra(straight or branched C1-C6 alkyl)phosphonium, or tri(C5-C8 cycloalkyl)-(straight or branched C1-C6 alkyl)phosphonium; or an ammonium cation, such as (but not limited to) tetra(straight or branched C1-C6 alkyl)ammonium, and tri(C5-C8 cycloalkyl)-(straight or branched C1-C6 alkyl)ammonium.

[0160] Item 31: An electrochromic composition as described in any of items 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, wherein the polymeric thickener comprises a polymer, wherein the polymer comprises at least one of the following: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)) or poly(linear or branched C1-C8 alkyl)(meth)acrylate).

[0161] Item 32: An electrochromic composition as described in any of items 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or 31, wherein the solvent comprises at least one of the following: ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, cyclopentane, α,ω-(C2-C8) dinitrile or di(straight or branched C1-C8) acetamide.

[0162] Item 33: A compound represented by the following formula (IIa), Where R 2 is selected from a divalent straight or branched alkane linking group; and R 3 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

[0163] Item 34: The compound according to Item 33, wherein R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0164] Item 35: The compound according to Item 33 or Item 34, wherein R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0165] Item 36: A salt comprising an anion represented by the following formula (II), Where R 1 is selected from a divalent straight or branched alkane linking group; and R 2 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

[0166] Item 37: The salt of Item 36, wherein for the anion represented by formula (II), R 2 Selected from divalent straight or branched C1-C 10 An alkane linker group, and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

[0167] Item 38: The salt of Item 36 or Item 37, wherein for the anion represented by formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

[0168] Item 39: The salt of any one of items 36, 37 or 38, wherein the salt further comprises a counter cation.

[0169] Item 40: The salt of Item 39, wherein each counter cation is independently selected from an optionally substituted nitrogen-containing aliphatic heterocyclic ammonium cation, an optionally substituted nitrogen-containing aromatic heterocyclic ammonium cation, a tetrasubstituted ammonium cation, or a combination thereof.

[0170] Item 41: A salt according to Item 39 or Item 40, wherein each counter cation is selected from a tetrasubstituted ammonium cation represented by the following formula (B), Formula (B) Where R a , R b , R c and R d Each is independently selected from a linear or branched alkyl group, an unsubstituted cycloalkyl group, a substituted cycloalkyl group, an unsubstituted aryl group and a substituted aryl group.

[0171] Item 42: The salt of Item 41, wherein R a , R b , R c and R d Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0172] Item 43: A salt according to Item 41 or Item 42, wherein R a , R b , R c and R d Each independently selected from a linear or branched C1-C 10 alkyl.

[0173] Item 44: A salt as in any one of items 36, 37, 38, 39, 40, 41, 42 or 43, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0174] Item 45: A salt according to any one of Items 36, 37, 38, 39, 40, 41, 42, 43 or 44, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

[0175] The present invention is more particularly described in the following examples, which are intended to be illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Example

[0176] In the following examples, in part-1, the synthesis of the anode component anion of the anode component and the salt according to the present invention is described. In part-2, the preparation of the electrochromic device according to the present invention is described. In part-3, the evaluation of the electrochromic device of part-2 is described. Part-1 Synthesis Example 1

[0177] A non-limiting illustration of the preparation of an anode component anion represented by formula (I) according to the present invention is provided with reference to the following Scheme-(1), wherein R 1 It is a divalent n-propane linking group.

[0178] To a dried 3-necked, 500 ml round bottom flask with a magnetic stirrer was added 200 ml of dimethylformamide (DMF) and 10 g of (1) phenoxazine (50.2 mmol). The solution was stirred for 1 hour while purging with nitrogen. 2.4 g of 60% NaH (60 mmol) was added to the reaction mixture. The solution was observed to turn dark red and bubbles were generated therein. After mixing under nitrogen for one hour, bubbles were observed to cease. Under nitrogen purge, 6.6 g of (2) 1,3-propane sultone (55.2 mmol) dissolved in 10 g of anhydrous DMF was added dropwise to the contents of the flask. After the addition of (2) 1,3-propane sultone was completed, the reaction mixture was stirred at room temperature under nitrogen for 18 hours.

[0179] The reaction was quenched by adding 100 mL of deionized (DI) water and the solvent was removed by applying vacuum, leaving an oily substance in the flask. To the oily substance was added 50 mL of ethyl acetate, which caused a precipitate to form, which was collected by vacuum filtration. The precipitate was washed with cold ethyl acetate and dried overnight at 60° C. in vacuum to give the desired product (3) sodium 3-(10H-phenoxazine-10-yl)-propane-1-sulfonate as an off-white solid. Process-(1) Synthesis Example 2

[0180] A non-limiting illustration of the preparation of an anode component anion represented by formula (II) according to the present invention is provided with reference to the following Scheme-(2), wherein R 2 is a divalent n-propane linking group and R 3 It is trifluoromethyl.

[0181] (3) Sodium 3-(10H-phenoxazine-10-yl)-propane-1-sulfonate was prepared according to Synthesis Example 1. One gram (0.0029 mol) of (3) sodium 3-(10H-phenoxazine-10-yl)propane-1-sulfonate was finely ground with a mortar and pestle and then placed in a 100 mL round-bottom flask equipped with a magnetic stirring bar and a reflux condenser under a N2 purge / atmosphere. A 20 ml amount of acetone and 40 mg of 18-crown-6 ether were added to the flask and the mixture was stirred vigorously for 15 minutes. The solution became cloudy, but the presence of solid sodium salt (3) was observed. Under N2, (4) cyanuric chloride (540 mg, 0.0029 mol, 1 eq.) was added with vigorous stirring. The mixture was refluxed on an oil bath (at about 80°C) for 24 hours. The color of the solution turned orange and a fine precipitate was formed. No bulk of the initial Na salt (3) was observed. Thin layer chromatography (TLC) confirmed the presence of a single reaction product, which turned pink in air upon exposure to shortwave (316 nm) UV, demonstrating the formation of (5) 3-(10H-phenoxazine-10-yl)-propane-1-sulfonyl chloride. The product (5) had high fluidity in 50:50 EtOAc / hexane. The reaction mixture was cooled to room temperature and filtered through a thin layer of alumina. The solvent was removed in vacuo to give 1.25 g of an orange-yellow glassy solid (5). The product (5) was dissolved in MeCN and the solid was filtered off. The filtrate was used in the next step without additional purification.

[0182] (6) trifluoromethylsulfonamide (4.53 g, 0.0305 mol, 1.05 equiv) and potassium carbonate (40 g, 0.29 mol, 10 equiv) were placed in a 500 ml 3-necked flask equipped with a reflux condenser, a magnetic stirring bar and a fritted Schlenk funnel. The nitrogen feed port was connected to the condenser and the Schlenk funnel and fixed with a plastic clip. The container was flushed with a strong nitrogen stream for 15 seconds and a septum was installed in the remaining neck. Anhydrous MeCN in an amount of 100 ml was added through the septum using a syringe. The mixture was vigorously stirred for 20 minutes to produce a white turbid dispersion. 50 ml of anhydrous MeCN was added to the crude (5) 3-(10H-phenoxazine-10-yl)propane-1-sulfonyl chloride (9.84 g, 0.029 mol) (filtrate of the previous step) under a nitrogen stream and the resulting solution was transferred to a Schlenk funnel. The Schlenk funnel was purged with nitrogen and plugged with a stopper secured by a clamp. A solution of MeCN and (5) 3-(10H-phenoxazine-10-yl)propane-1-sulfonyl chloride was added dropwise to a 3-necked flask at room temperature over a period of one hour. The contents of the 3-necked flask were refluxed for 24 hours. The formation of a bulk precipitate was observed. The precipitate was filtered off and the resulting solution was concentrated in vacuo. The residue was recrystallized from water to give the product (7) 3-(10H-phenoxazine-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonamide potassium as brown needles. Process-(2) Part-2

[0183] The electrochromic device according to the present invention was prepared according to the following procedure. The following initial solution was prepared under magnetic stirring: propylene carbonate (7 g); ethylene carbonate (3 g); 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonyl imide (EMIM-TFSI) (1 g); 3-(10H-phenoxazine-10-yl)-N-trifluoromethanesulfonylpropane-1-sulfonamide potassium (PTTK) (100 mg); and 1,1'-diethyl-4,4'-bipyridinium bis(trifluoromethane)sulfonyl imide (diethylviologen TFSI) (100 mg). 3.5 g of polyacrylonitrile was added to the initial solution, followed by homogenization, causing the formation of a viscous slurry. A liquid film of the viscous slurry having a thickness of 400 micrometers (μm) was formed on a sacrificial polyethylene terephthalate (PET) liner using a spatula. The liquid film was heated to 70°C for 10 minutes, causing the formation of a cured film / layer, which was the electrochromic layer. The cured film / electrochromic layer was separated from the sacrificial / temporary liner, cut to a size (2"×3"; 5.08 cm×7.62 cm), and placed on a fluorine-doped tin oxide (FTO)-glass electrode (3"×4"; 7.62 cm×10.16 cm), which already had a copper tape covered with insulating polyimide wrapped around the edges. A pre-made thermoplastic gasket of 0.5" (1.27 cm) width and 400 microns thickness was added, surrounding the active area. A second fluorine-doped tin oxide (FTO)-glass was placed on the electrochromic layer. The stack was subjected to vacuum lamination at 140°C for 15 minutes to completely melt and seal the gasket. After cooling, the electrochromic device thus formed was removed from the vacuum lamination apparatus. Part-3

[0184] The relationship between the percent transmission and wavelength (nm) of the electrochromic device of Part-2 in the transparent / unactivated state and the dark / activated state (in each case, at room temperature) is plotted in FIG. Figure 2 Reference Figure 2 , electrochromic devices according to the present invention provide a significant and desirable level of darkening (i.e., reduction in visible light transmission) when activated, compared to the transparent / unactivated state. Figure 2 The electrochromic device of Part-2 is described as a "PTTK-ethylviologen device". Figure 2 : The transmission percentage versus wavelength curve in the transparent / unactivated state is labeled "PTTK-EV, transparent"; and the transmission percentage versus wavelength curve in the darkened / activated state is labeled "PTTK-EV, dark".

[0185] The invention has been described with reference to specific details of specific embodiments thereof. Such details are not intended to be construed as limiting the scope of the invention except as included in the appended claims.

Claims

1. An electrochromic device, comprising: (a) a first substrate having a surface including a first transparent electrode layer; (b) a second substrate having a surface including a second transparent conductive electrode layer, wherein the first transparent electrode layer and the second transparent electrode layer are spaced apart from each other; and (c) an electrochromic layer inserted between the first transparent conductive electrode layer and the second transparent conductive electrode layer, wherein the electrochromic layer comprises: (i) cathode components, (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by the following formula (I) or formula (II): Wherein for formula (I), R 1 is selected from divalent straight or branched alkane linking groups, and Wherein for formula (II), R 2 is selected from divalent straight or branched alkane linking groups, and R 3 is selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl, (iii) optionally an electrolyte, and (iv) Polymer matrix.

2. The electrochromic device of claim 1, wherein for formula (I), R 1 Selected from divalent straight or branched C1-C 10 an alkane linking group, and Wherein for formula (II), R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

3. The electrochromic device of claim 2, wherein for formula (I), R 1 is selected from divalent straight or branched C1-C5 alkyl groups, and Wherein for formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

4. The electrochromic device of claim 1, wherein the anode component further comprises a counter cation.

5. An electrochromic device as claimed in claim 4, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

6. The electrochromic device of claim 5, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

7. The electrochromic device of claim 1, wherein the cathode component comprises at least one of: a 1,1'-disubstituted-4,4'-bipyridinium cation represented by the following formula (III), or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted-4,4'-bipyridinium) cation represented by the following formula (VI): Wherein for formula (III), R 4 and R 5 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and Wherein for formula (IV), R 6 and R 8 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and R 7 Selected from divalent straight or branched C1-C 10 Alkane linking group.

8. The electrochromic device of claim 7, wherein for formula (III), R 4 and R 5 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and Wherein for formula (IV), R 6 and R 8 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and R 7 Selected from divalent straight or branched C1-C8 alkane linking groups.

9. The electrochromic device of claim 7, wherein the cathode component further comprises counter anions, wherein each counter anion of the cathode component is selected from BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C - and B(phenyl)4 - .

10. The electrochromic device of claim 1, wherein the electrolyte is present and comprises: at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide, and At least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(straight chain or branched C1-C6 alkyl)-3-(straight chain or branched C1-C6 alkyl)imidazolium, 1-(straight chain or branched C1-C6 alkyl)-1-(straight chain or branched C1-C6 alkyl)piperidinium, tetra(straight chain or branched C1-C6 alkyl)ammonium or tri(C5-C8 cycloalkyl)-(straight chain or branched C1-C6 alkyl)ammonium.

11. The electrochromic device of claim 1 , wherein the polymer matrix comprises a polymer, wherein the polymer comprises at least one of: poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)) or poly((linear or branched C1-C8 alkyl)(meth)acrylate).

12. An electrochromic composition comprising: (i) cathode components, (ii) an anode component comprising an anode component anion selected from at least one anode component anion represented by the following formula (I) or formula (II): Wherein for formula (I), R 1 is selected from divalent straight or branched alkane linking groups, and Wherein for formula (II), R 2 is selected from divalent straight or branched alkane linking groups, and R 3 is selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl, (iii) optionally an electrolyte, (iv) polymeric thickeners; and (v) Solvent.

13. The electrochromic composition of claim 12, wherein for formula (I), R 1 Selected from divalent straight or branched C1-C 10 an alkane linking group, and Wherein for formula (II), R 2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

14. The electrochromic composition according to claim 13, wherein for formula (I), R 1 is selected from divalent straight or branched C1-C5 alkyl groups, and Wherein for formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

15. The electrochromic composition of claim 12, wherein the anode component further comprises a counter cation.

16. The electrochromic composition of claim 15, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

17. The electrochromic composition of claim 16, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

18. The electrochromic composition of claim 12, wherein the cathode component comprises at least one of: a 1,1'-disubstituted-4,4'-bipyridinium cation represented by the following formula (III), or a 1,1-(alkane-α,ω-diyl)-bis-(1'-substituted-4,4'-bipyridinium) cation represented by the following formula (VI): Formula (III) Formula (IV) Wherein for formula (III), R 4 and R 5 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and Wherein for formula (IV), R 6 and R 8 Each independently selected from a linear or branched C1-C 10 alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted aryl and substituted aryl, and R 7 Selected from divalent straight or branched C1-C 10 Alkane linking group.

19. The electrochromic composition of claim 18, wherein for formula (III), R 4 and R 5 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and Wherein for formula (IV), R 6 and R8 are each independently selected from a linear or branched C1-C4 alkyl group, an unsubstituted phenyl group and a substituted phenyl group, and R 7 Selected from divalent straight or branched C1-C8 alkane linking groups.

20. The electrochromic composition of claim 18, wherein the cathode component further comprises a counter anion, wherein each counter anion of the cathode component is selected from BF4 - PF6 - 、ClO4 - CF3SO3 - 、(CF3SO2)2N - 、(CF3SO2)3C - and B(phenyl)4 - .

21. The electrochromic composition of claim 12, wherein the electrolyte is present and comprises: at least one electrolyte anion, wherein each electrolyte anion is independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide, and At least one electrolyte cation, wherein each electrolyte cation is independently selected from 1-(straight chain or branched C1-C6 alkyl)-3-(straight chain or branched C1-C6 alkyl)imidazolium, 1-(straight chain or branched C1-C6 alkyl)-1-(straight chain or branched C1-C6 alkyl)piperidinium, tetra(straight chain or branched C1-C6 alkyl)ammonium or tri(C5-C8 cycloalkyl)-(straight chain or branched C1-C6 alkyl)ammonium.

22. The electrochromic composition of claim 12, wherein the polymeric thickener comprises a polymer, wherein the polymer comprises at least one of poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C1-C6 alkylene)) or poly((linear or branched C1-C8 alkyl)(meth)acrylate).

23. The electrochromic composition of claim 12, wherein the solvent comprises at least one of the following: ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, cyclopentane sulfone, α,ω-(C2-C8) dinitrile or di(straight or branched C1-C8) acetamide.

24. A compound represented by the following formula (IIa): Where R 2 is selected from a divalent straight or branched alkane linking group; and R 3 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

25. The compound of claim 24, wherein R2 Selected from divalent straight or branched C1-C 10 an alkane linking group; and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl or linear or branched C1-C 10 Perfluorinated alkyl.

26. The compound of claim 25, wherein R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

27. A salt comprising an anion represented by the following formula (II): Where R 1 is selected from a divalent straight or branched alkane linking group; and R 2 Selected from fluorine, linear or branched fluorinated alkyl or linear or branched perfluorinated alkyl.

28. The salt of claim 27, wherein for the anion represented by formula (II), R 2 Selected from divalent straight or branched C1-C 10 An alkane linker group, and R 3 Selected from fluorine, straight chain or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 Perfluorinated alkyl.

29. The salt of claim 28, wherein for the anion represented by formula (II), R 2 is selected from a divalent straight or branched C1-C5 alkane linking group; and R 3 Selected from linear or branched C1-C5 perfluorinated alkyl groups.

30. The salt of claim 27, wherein the salt further comprises a counter cation.

31. The salt of claim 30, wherein each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations.

32. The salt of claim 31, wherein each counter cation is independently selected from tetra(straight or branched C1-C 10 alkyl)ammonium cation.

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