Electrochromic devices and compositions including anodic component anions

Abstract

The present invention relates to electrochromic devices and compositions, the anodic component of which comprises an anodic component anion selected from at least one anodic component anion represented by formula (I) or (II) below: [Formula 1] JPEG2025514934000031.jpg11880 With reference to formulas (I) and (II), R 1 and R 2 are each independently selected from divalent linear or branched alkane linking groups. 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. The present invention also relates to salts containing an anion of formula (II). The present invention further relates to neutral compounds corresponding to formula (II) in which hydrogen (H) is bonded to the nitrogen anion.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the right to and priority to U.S. Provisional Patent Application No. 63 / 333,182, filed April 21, 2022, and U.S. Nonprovisional Patent Application No. 18 / 133,559, filed April 12, 2023, the disclosures of which, in each case, are incorporated herein by reference in their entireties.

[0002] Field The present invention relates to electrochromic devices and compositions that include an anodic component anion, where the anion is covalently bonded to an anodic component or group. [Background technology]

[0003] Electrochromism involves a reversible change in the visible color and / or transmittance of a material by the application of an electric potential. The change in color and / or transmittance typically involves alternating cycles of oxidized and reduced charge states. In general, materials that produce color upon reduction are referred to as cathodically coloring electrochromic materials, and materials that produce color upon oxidation are referred to as anodically coloring electrochromic materials.

[0004] Electrochromic devices typically include opposing electrodes (e.g., an anode and a cathode) with a solution or gel-based electrochromic layer interposed therebetween. The kinetics of such electrochromic devices are typically governed primarily by mass transport of cathodic and anodic components across the electrochromic layer. Due to charge conversion, the currents of both electrodes are necessarily equal. If one of the components (cathodic or anodic components) moves or is transported more slowly through or across the electrochromic layer, typically a higher concentration of that component is required, more specifically, a higher concentration gradient (higher interfacial concentration) of the slower moving / transported component at the electrode interface is required to equalize the diffusion flux and maintain a given current. Adjusting and / or maintaining a higher concentration of the component with reduced mass transport may require additional preparation and / or manufacturing steps and may result in inadvertent formulation errors. Mass transport imbalances may, in some cases, result in reduced durability of the electrochromic device, especially if the slower mass transporting active component undergoes over-oxidation or over-reduction at a particular electrode.

[0005] Factors that contribute to the reduction of mass transport of a component and the corresponding mass transport imbalance between components include, but are not limited to, the reduction of the solubility of the component in the electrochromic layer and / or the lack of charge associated therewith.In some electrochromic devices, the cathode component has a positive charge and a counter anion associated therewith, while the anode component has no charge associated therewith.The lack of charge associated with the anode component can contribute to the undesirable mass transport imbalance to the cathode component.

[0006] It would be desirable to develop new electrochromic devices and compositions whose active components, particularly the cathodic and anodic components, provide improved mass transport balance. It would further be desirable for such newly developed electrochromic devices and compositions to provide or be otherwise associated with improved durability, reduced manufacturing and / or operating costs, and / or improved operational efficiency. Summary of the Invention

[0007] According to the present invention, there is provided 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 being spaced apart from each other in opposing positions; and (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer. The electrochromic layer comprises: (i) a cathode component; and (ii) a compound represented by the following formula (I) or (II): [ka] and an anode component comprising an anode component anion selected from at least one anode component anion represented by the formula: With reference to formula (I), R 1 is selected from divalent linear or branched alkane linking groups. 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, a linear or branched fluorinated alkyl, or a 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 further 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] According to the present invention, furthermore, a compound represented by the following formula (IIa): [ka] The compound is represented by the formula: With reference to formula (IIa), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

[0010] According to the present invention, a compound represented by the following formula (II): [ka] Further provided is a salt comprising an anion represented by: With reference to formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

[0011] The features which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. These and other features of the invention, its operating advantages, and certain objects attained by its uses will be more fully understood from the following detailed description, in which non-limiting embodiments of the invention are shown and described. [Brief description of the drawings]

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

[0013] [Diagram 2] 1 is a graphical representation of a plot of % transmission versus wavelength obtained from an electrochromic device according to the present invention in an activated (dark) and non-activated (light) state, as described in the Examples herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In Figures 1 and 2, like characters sometimes refer to the same components and / or elements unless otherwise stated.

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

[0016] Unless otherwise stated, all ranges or ratios disclosed herein should be understood to encompass any and all values ​​and subranges or subratios subsumed therein. For example, a range or ratio described as "1 to 10" should be considered to include any and all values ​​therebetween (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), and subranges between (and including) the minimum value of 1 and the maximum value of 10, i.e., without limitation, all subranges or subratios beginning with a minimum value of 1 or greater and ending with a maximum value of 10 or less, such as 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0017] As used herein, unless otherwise specified, a left-to-right representation of a linking group, such as a divalent linking group, includes other suitable orientations, such as, but not limited to, a right-to-left orientation. [ka] or equivalently, the left-to-right representation of -C(O)O- is its right-to-left representation [ka] or equivalently, -O(O)C- or -OC(O)-.

[0018] Except in the operating examples, or unless otherwise expressly stated, 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) of a polymer (ie, Mw / Mn).

[0021] As used herein, the term "polymer" refers to homopolymers (eg, prepared from a single monomeric type), copolymers (eg, prepared from at least two monomeric types), and graft polymers.

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

[0023] As used herein, the term "electrochromic" and similar terms such as "electrochromic compound" refer to having an absorption spectrum of at least visible radiation that changes in response to the application of an electric potential. Additionally, as used herein, the term "electrochromic material" refers to any substance that is adapted to exhibit electrochromic properties (e.g., adapted to have an absorption spectrum of at least visible radiation that changes in response to an applied electric potential) and that includes at least one electrochromic compound.

[0024] As used herein, the term "electric potential" and related terms such as "electrical potential" refer to an electrical potential that can induce a response in a material, such as, but not limited to, transforming an electrochromic material from one form or state to another, as described in more detail herein.

[0025] The terms "first" and "second", when used herein to modify the term "state", are not intended to refer to a particular order or chronological sequence, but instead refer to two different conditions or properties. For purposes of non-limiting illustration, the first and second states of an electrochromic compound, such as anodically colored electrochromic compound, may differ with respect to at least one optical property, such as, but not limited to, the absorption of visible radiation and / or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, an anodically colored electrochromic compound of the present invention may have different absorption spectra in each of the first and second states. For example, but not limited to, herein, an anodically colored electrochromic compound may be transparent in the first state and colored in the second state. Alternatively, an anodically colored 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 words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors, and security elements such as security marks.

[0027] As used herein, the term "window" means an opening adapted to permit the transmission of radiation. Non-limiting examples of windows include automobile and aircraft transparencies, windshields, filters, shutters, and optical switches.

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

[0029] As used herein, spatial or directional terms such as "left," "right," "inside," "outside," "upper," "lower," and the like, refer to the present invention as shown in the drawings. However, it should be understood that the present invention can assume various alternative orientations, and thus such terms should not be considered limiting.

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

[0031] As used herein, the terms "intervening" and "intervening between" mean present or disposed between, but not necessarily in direct (or abutting) contact with, an overlying and / or underlying element or surface thereof. For example, an "intervening" layer 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 intervening layer and the first and / or second substrate.

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

[0033] As used herein, the recitation of "straight chain or branched" groups, such as straight chain or branched alkyl, is defined herein as follows: methylene or methyl groups; linear groups, e.g., linear C-C alkyl groups; 20 Alkyl groups; and appropriately branched groups, such as branched C-C 20 It is understood to include alkyl groups.

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

[0035] As used herein, the term "heterocycloalkyl" refers to a suitably cyclic group, such as, but not limited to, C2-C 12 Heterocycloalkyl groups, such as C2-C 10 Heterocycloalkyl groups, such as C5-C7 heterocycloalkyl groups, have at least one heteroatom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl, and piperidinyl. The term "heterocycloalkyl" as used herein also includes bridged-ring polycyclic heterocycloalkyl groups, such as, but not limited to, 7-oxabicyclo[2.2.1]heptanyl; and fused-ring polycyclic heterocycloalkyl groups, such as, but not limited to, octahydrocyclopenta[b]pyranyl and octahydro-1H-isochromenyl.

[0036] The descriptions, classes, and examples provided herein with respect to alkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkyl groups, and the like, are also applicable to alkane groups, cycloalkane groups, heterocycloalkane groups, haloalkane groups, and the like, including, but not limited to, polyvalent alkane groups, e.g., polyvalent alkane linking groups, e.g., divalent alkane linking groups.

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

[0038] The term "heteroaryl" as used herein includes, but is not limited to, C-C 18 Heteroaryl, for example, but not limited to, C-C 10 Heteroaryl (including fused-ring polycyclic heteroaryl groups) refers to an aryl group having at least one heteroatom in an aromatic ring or, in the case of a fused-ring polycyclic heteroaryl group, in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, 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] The term "nitrogen-containing heterocycle", e.g., "nitrogen-containing heterocyclic group" or nitrogen-containing heterocyclic substituent", as used herein, includes, but is not limited to, nitrogen-containing rings to which the nitrogen-containing ring is attached via a ring nitrogen. Examples of nitrogen-containing heterocycles include, but are not limited to, aliphatic cyclic amino (or alicyclic amino), such as morpholino, piperidino, pyrrolidino, and decahydroisoquinolino; and heteroaromatics, such as imidazole, pyrrole, indole, and carbazole.

[0041] As used herein, the recitation of "substituted" groups refers to groups including, but not limited to, alkyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, and / or heteroaryl groups, in which at least one hydrogen has been replaced with a group or "substituent" other than hydrogen, such as, but not limited to, alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; carboxylate groups; carboxylic acid groups; phosphoric acid groups; phosphate ester groups; sulfonic acid groups; sulfonate ester groups; nitro groups; cyano groups; alkyl groups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups (including alkaryl groups, hydroxyl substituted aryls such as phenols, poly-fused ring aryls); aralkyl groups; heteroaryl groups (including poly-fused ring heteroaryl groups); amino groups, such as -N(R 11’ )(R 12’ ), where R 11’ and R 12’ are each independently selected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, or heteroaryl; a carboxylate group; a siloxane group; an alkoxysilane group; a polysiloxane group; an amide group; a carbamate group; a carbonate group; a urea group; a trialkylsilyl group; a nitrogen-containing heterocycle; or combinations thereof, classes and examples as further described herein, etc. According to some embodiments of the present invention, the substituents of the substituted groups are more specifically recited.

[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 radical, such as -F, -Cl, -Br, and -I.

[0043] As used herein, the recitation of "halo-substituted" and related terms (e.g., but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, and haloheteroaryl) refers to a group in which at least one and up to all of its available hydrogen radicals are replaced with a halo group, such as, but not limited to, F, Cl, or Br. The term "halo-substituted" includes "perhalo-substituted." As used herein, the term perhalo-substituent and related terms (e.g., but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl, or perhaloheteroaryl) refers to a group in which all of its available hydrogen radicals are replaced with a halo group. For non-limiting illustrative purposes, perhalomethyl is -CX3 and perhalophenyl is -CX5, 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" is synonymous with "one or more," regardless of whether the elements are listed conjunctively or disjunctively. For example, the phrases "at least one of A, B, and C" and "at least one of A, B, or C" refer to any one of A, B, or C, or any combination of two or more of A, B, or C, respectively. 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 "chosen from," regardless of whether the elements are listed conjunctively or disjunctively. Additionally, the phrases "selected from A, B, and C" and "selected from A, B, or C" refer to any one of A, B, or C, respectively, or any combination of 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 description of the invention herein may describe certain features as "particularly" 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 present disclosure.

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

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

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

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

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

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

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

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

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

[0056] As used herein, and according to some embodiments, the term "alkoxysilane" with respect to groups and substituents of various groups of the compounds and components of the present invention, and related terms such as "alkoxysilane group" and alkoxysilane substituents, refers to -Si(OR''). w (R) t wherein w is 1 to 3, t is 0 to 2, with the proviso that the sum of w and t is 3, R″ for each w is independently selected from alkyl, and R for each t is independently selected from the groups described below other than hydrogen.

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

[0058] With reference to formula (A), t' is 2 or more, for example, 2 to 200, and R f and R g are each independently selected from the group R described below other than hydrogen; R h are independently a group R described below.

[0059] Unless otherwise specified, each R group of each of the above ketone, ester (carboxylic acid ester), carboxylate, amide, carbonate, carbamate, urea, siloxane, alkoxysilane, and polysiloxane groups is independently selected in each occurrence from hydrogen, alkyl, haloalkyl, perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof, including the classes and examples thereof listed herein above.

[0060] In some embodiments, references herein to a counterion (such as a countercation and / or a counteranion) of a component refer to the counterion of the component when prepared separately from and / or prior to combination 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) comprises an anode component, the anode component comprising 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 comprising an anode moiety (group or site), such as a (10H-phenothiazin-10-yl) site, and an anion, such as a sulfonate anion or a triflamide anion, covalently bonded to the anode site. In some further embodiments, the anion of the anode component anion is covalently bonded to the anode group or site by a divalent linear or branched alkane linking group. In some further embodiments, the anode component anion is an anode-colored electrochromic compound or a group having an anion covalently bonded thereto.

[0062] According to some embodiments of the present invention, with reference to the anode component anion represented by formula (I), R 1 is a divalent linear or branched C1-C 10 The linking groups are selected from alkane linking groups.

[0063] In some embodiments, with reference to the anode component anion represented by Formula (II), R 2 is a divalent linear or branched C1-C 10 alkane linking groups; R 3 is fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

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

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

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

[0067] According to some further embodiments, the anode component comprising the anode component anion further comprises a counter cation. Classes and examples of cations from which each counter cation may 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, e.g. 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, which are described in more detail below. The optional substituents of the classes and examples of ammonium cations can be selected from the classes and examples of substituents listed herein above, such as, but not limited to, linear or branched alkyl groups, cycloalkyl groups and aryl groups. The N-substituents and N,N-disubstituents of the ammonium cations can be selected from the classes and examples of substituents listed herein above, such as, but not limited to, linear or branched alkyl groups, cycloalkyl groups and aryl groups.

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

[0069] Referring to formula (B), R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl. With further reference to formula (B), R a , R b , R c and R d are each independently linear or branched C1 to C10 The substituents of the substituted cycloalkyl and substituted phenyl groups can be independently selected from those listed herein above, such as, but not limited to, linear or branched alkyl groups, cycloalkyl groups, and aryl groups.

[0070] In some embodiments, with reference to Formula (B), R a , R b , R c and R d In some further embodiments, each of R in formula (B) is independently selected from linear or branched alkyl. a , R b , R c and R d Each of the linear or branched C1 to C 10 alkyl.

[0071] In some embodiments, each countercation of the anode components is independently selected from tetra(linear or branched alkyl)ammonium cations. In some further embodiments, each countercation of the anode components is independently selected from tetra(linear or branched C1-C 10 alkyl) ammonium cations.

[0072] In some embodiments, the anode component is composed of or otherwise consists of anode component anions selected from at least one anode component anion represented by Formula (I) or Formula (II) and countercations, where the anode component has an equal number of anions and countercations and a corresponding neutral charge.

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

[0074] According to some embodiments, in addition to the anodic component anion having a covalently bound anion, for example represented by Formula (I) and / or Formula (II), the anodic component of the electrochromic layer may further comprise one or more additional anodic electrochromic compounds, such as, but not limited to, ferrocene and / or ferrocene derivatives, at least one of which is substituted with at least one substituent, including those listed herein above; 5,10-dihydro-5,10-di(linear 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 additional anodic electrochromic component is present in an amount of 1 wt.% to 50 wt.%, 1 wt.% to 25 wt.%, or 1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.%, each percent weight being based on the total weight of the anodic component anion and the additional anodic electrochromic component. According to some embodiments, when an additional anodic component is present (in addition to the anodic component anion having a covalently bonded anion), an additional cathodic component (or additional suitable amounts of cathodic components) may also be present. In some embodiments, the additional cathodic component comprises one or more cathodic components represented by formula (III) and / or (IV).

[0075] In some embodiments, the cathode component of the electrochromic layer of an electrochromic device comprises at least one 1,1'-disubstituted-4,4'-dipyridinium cation represented by formula (III) below, or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by formula (VI) below. Formula (III) [ka] Formula (IV) [ka]

[0076] With reference to formula (III), R 4 and R 5 are each independently linear or branched C1 to C 10 It is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl.

[0077] Referring to formula (IV), according to some embodiments, R 6 and R 8 are each independently linear or branched C1 to C 10 is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C1-C 10 The linking groups are selected from alkane linking groups.

[0078] R in formula (III) 4 and R 5 and R in formula (IV) 6 and R 8 The aryl groups of the unsubstituted and substituted aryl groups from which each may be independently selected include those aryl groups listed herein above, such as, but not limited to, phenyl, naphthyl, phenanthryl, and anthracenyl. 4 and R 5 and R of formula (IV) 6 and R 8 The cycloalkyl groups of the unsubstituted and substituted cycloalkyl groups, each of which may be independently selected, include those cycloalkyl groups listed herein above, such as, but not limited to, cyclopentyl, cyclohexyl, and cycloheptyl.

[0079] R in formula (III) 4 and R 5and R of formula (IV) 6 and R 8 Substituents for the substituted cycloalkyl and aryl groups, each of which may be independently selected, include those listed herein above. In some embodiments, R 4 and R 5 and R of formula (IV) 6 and R 8 Each of the substituents of the substituted cycloalkyl and aryl groups, each of which may be independently selected, is each independently selected from alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiol groups; alkylthio groups; arylthio groups; ketone groups; aldehyde groups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups; aryl groups; aralkyl groups (e.g., benzyl groups); heteroaryl groups; and amino groups.

[0080] R in formula (III) 4 and R 5 and R of formula (IV) 6 and R 8 Straight-chain or branched alkyl groups from which each may be independently selected include the classes and examples of alkyl groups listed hereinabove, such as, but not limited to, methyl, ethyl, straight-chain or branched propyl, straight-chain or branched butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, and straight-chain or branched heptyl.

[0081] With further reference to formula (III), according to some embodiments of the present invention, R 4 and R 5 are each independently selected from straight chain or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl.

[0082] With further reference to formula (IV), according to some embodiments of the present invention, R 6 and R 8 are each independently selected from linear or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl; R 7is selected from divalent linear or branched C1-C8 alkane linking groups. In some further embodiments, R 7 is a divalent linear or branched C1 to C5 alkane linking group, for example, a divalent linear or branched C3 to C5 alkane linking group.

[0083] According to some embodiments of the present invention, the cathode component further comprises a counter anion. In some further embodiments, the cathode component comprises an equal number of cations and counter anions (or anions), such that the cathode component has a corresponding net neutral charge. In some embodiments, each counter anion of the cathode component is BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , or B(phenyl)4 - In some embodiments, the counter anion of the cathodic component does not include or is not selected from the anodic component anions as represented by formulas (I) and (II).

[0084] According to some embodiments of the present invention, the cathode component is present in the electrochromic layer in an amount of 0.25 wt % to 6.25 wt %, or 0.5 wt % to 5 wt %, or 1 wt % to 3 wt %, where the weight percentage in each case 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 comprises an electrolyte. In some embodiments, the electrolyte comprises at least one electrolyte anion and at least one electrolyte cation. In some embodiments, the electrolyte of the electrochromic layer comprises an equal number of electrolyte anions and electrolyte cations and has a corresponding net neutral charge.

[0086] In some embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion being independently selected from chloride, hexafluorophosphate, and bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imide. In some further embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte cation, each electrolyte cation being 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). 1-(linear or branched C1-C6 alkyl)ammonium; 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium; 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)pyrrolidinium; 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium; or a phosphonium cation, such as, but not limited to, tetra(linear or branched C1-C6 alkyl)phosphonium or tri(C5-C8 cycloalkyl)-(linear or branched C1-C6 alkyl)phosphonium.

[0087] In some embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion independently selected from bis(perfluoro(linear or branched C1-C6 alkylsulfonyl)imides, and at least one electrolyte cation, each electrolyte cation independently selected from 1-(linear or branched C1-C6 alkyl)-3-(linear or branched C1-C6 alkyl)imidazolium, 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)pyrrolidinium, or 1-(linear or branched C1-C6 alkyl)-1-(linear or branched C1-C6 alkyl)piperidinium.

[0088] In some further embodiments, the electrolyte of the electrochromic layer comprises at least one electrolyte anion, each electrolyte anion being a bis(trifluoromethylsulfonyl)imide, and at least one electrolyte cation, each electrolyte cation being 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 between 1% and 75% by weight, or between 5% and 50% by weight, or between 10% and 30% by weight, the weight percentage in each case being based on the total weight of the electrochromic layer.

[0090] According to some further embodiments, the electrochromic layer of the present invention includes a solvent. In some further embodiments, the solvent is present in the electrochromic layer instead of or in addition to the electrolyte. The solvent can include at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitriles, or di(linear or branched C1-C8) acetamides in some embodiments. Without intending to be bound by any theory, it is believed that according to some embodiments, the solvent acts, at least in part, as a plasticizer (or plasticizes) within the electrochromic layer. In some embodiments, the solvent is present in the electrochromic layer in an amount of 10% to 75% by weight or 20% to 60% by weight, the weight percentage in each case being 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. The polymer matrix, in some embodiments, is a gelled polymer matrix, a crosslinked polymer matrix, and / or a thermoplastic polymer matrix.

[0092] In some embodiments, the polymer matrix comprises a polymer, the polymer comprising 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).

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

[0094] The electrochromic layer of the electrochromic device of the present invention may further include one or more art-recognized optional additives, in some embodiments, including but not limited to thermal stabilizers, UV stabilizers, rheology modifiers, static colorants (such as static dyes and / or static pigments), kinetic additives (to promote electrode reactions), and combinations thereof. A non-limiting class of art-recognized thermal stabilizers is phenols, such as 2,6-ditertiarybutylphenol and compounds containing 2,6-ditertiarybutylphenol groups or moieties. A non-limiting class of art-recognized UV stabilizers is hindered amine light stabilizers (HALS), such as 2,2,6,6-tetramethylpiperidine and compounds containing 2,2,6,6-tetramethylpiperidine groups or moieties. Static colorants include colorants whose absorption spectrum does not change in response to actinic radiation (such as UV and / or visible light) or application of an electric potential, and do not include photochromic and electrochromic compounds. Non-limiting classes of kinetic additives include salts such as alkali and alkaline earth metal salts of perchlorates, tetrafluoroborates and hexafluorophosphates, as well as tetraalkylammonium salts. Non-limiting examples of rheology modifiers include dialkoxyacetophenones, such as 3',4'dimethoxyacetophenone, and optionally substituted cycloalkylarylketones, such as 1-hydroxycyclohexylphenylketone. Each optional additive can be present in any suitable active amount, such as 0.05% to 5% by weight, based on the total solids weight (including the weight of the optional additive) of the electrochromic layer.

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

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

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

[0098] With further reference to the electrochromic device (3) of FIG. 1, the first transparent electrode layer (20) and the second transparent electrode layer (32) are opposed in opposing positions relative to one another and in spaced apart relation.

[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 and in contact with the first transparent electrode layer (20) and the second transparent electrode layer (32).

[0100] The first and second substrates of the electrochromic device are, in some embodiments of the present invention, each independently selected from a transparent substrate. The transparent substrates from which the first and second substrates may be independently selected are, in some embodiments, made from 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 substrates from which the first and second substrates may be independently selected are made from materials including silica glass. The first and second substrates may, in some embodiments, each independently have any suitable thickness. In some embodiments, the first and second substrates may, in some embodiments, each independently have a thickness of 1 mm to 25 mm, or 2 mm to 10 mm.

[0101] The first and second transparent electrode layers of the electrochromic device of the present invention, in some embodiments, comprise 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(styrenesulfonate). The first and second transparent electrode layers, in some embodiments, may each independently be in the form of a grid of metal wires, a grid of carbon nanotubes, and / or a layer of graphene. In some embodiments, the first and second transparent electrode layers are each independently selected from semitransparent metal layers. In some further embodiments, one of the first and second transparent electrode layers includes (or is associated with) a reflective metal layer (e.g., including 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 devices of the present invention each independently comprise a conductive material selected from indium-tin-oxide, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), or a combination thereof.

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

[0104] Examples of articles, such as articles of manufacture, that may include or be defined by the electrochromic devices of the present invention include, but are not limited to, energy efficient and / or privacy transparent films (or windows), e.g., architectural and transportation transparent films or windows; mirrors, e.g., rearview mirrors; optical filters; ophthalmic articles, e.g., corrective lenses, non-corrective lenses, magnifying lenses, protective lenses, and visors; any other article or application where variable and controllable light transmission and / or color is desired.

[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 comprising 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 described herein above for the electrochromic layer of the electrochromic device of the invention.

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

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

[0109] According to some embodiments, in addition to the anodic component anion having a covalently bound anion, for example, represented by Formula (I) and / or Formula (II), the anodic component of the electrochromic composition may further comprise one or more additional anodic electrochromic compounds, such as, but not limited to, ferrocene and / or ferrocene derivatives, at least one of which is substituted with at least one substituent, including those listed herein above; 5,10-dihydro-5,10-di(linear 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 additional anodic electrochromic component is present in an amount of 1 wt.% to 50 wt.%, 1 wt.% to 25 wt.%, or 1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.%, each percent weight being based on the total weight of the anodic component anion and the additional anodic electrochromic component. According to some embodiments, when an additional anodic component is present (in addition to the anodic component anion having a covalently bonded anion), an additional cathodic component (or additional suitable amounts of cathodic components) may also be present. In some embodiments, the additional cathodic component comprises one or more cathodic components represented by formula (III) and / or (IV).

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

[0111] The polymeric thickener of the electrochromic composition, in some embodiments, comprises a polymer, the polymer comprising 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.

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

[0113] The electrochromic compositions of the present invention include a solvent. In some embodiments, the solvent of the electrochromic composition includes at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitriles, or di(linear or branched C1-C8) acetamide.

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

[0115] According to some embodiments, the anode component comprising the anode component anion further comprises a counter cation. The class and examples of cations from which each counter cation is derived may be independently selected from the classes and examples listed herein above with respect to electrochromic devices. In some embodiments of the electrochromic composition of the present invention, each counter cation is independently selected from tetra(linear or branched alkyl)ammonium cations. According to some further embodiments, each counter cation is independently selected from tetra(linear or branched C1-C 10 alkyl) ammonium cations.

[0116] In some embodiments, the cathode component of the electrochromic composition further comprises a counter anion, and each counter anion of the cathode component is BF4. - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , and B(phenyl)4 - In some embodiments, the counter anion of the cathodic component of the electrochromic composition does not include or is not selected from the anodic component anions as represented by formulas (I) and (II).

[0117] The electrochromic compositions of the present invention may, in some embodiments, include one or more art-recognized optional additives, such as, but not limited to, thermal stabilizers, UV stabilizers, rheology modifiers, static colorants (such as static dyes and / or static pigments), kinetic additives (to promote electrode reactions), and combinations thereof. The optional additives, in each case, are as described hereinabove with respect to the electrochromic devices of the present invention. Each optional additive may be present in the electrochromic composition in any suitable active amount (e.g., 0.05% to 5% by weight) based on the total weight of the electrochromic composition (including the weight of the optional additives).

[0118] According to some embodiments of the present invention, the electrochromic layer of an electrochromic device is formed from the electrochromic composition of the present invention. According to some embodiments of the present invention, the formation of the electrochromic composition and electrochromic layer includes the following steps: First, all components of the electrochromic composition except the polymeric thickener are mixed under shear (e.g., with an impeller) until a homogenous mixture is formed. Second, the polymeric thickener is added and the combination is subjected to homogenization, resulting in the formation of a thick slurry. Using a doctor blade or drawdown bar or the like, a liquid film of the thick slurry is formed on a sacrificial or temporary liner (composed of polyethylene terephthalate in some embodiments). The liquid film, while on the sacrificial / temporary liner, is subjected to an elevated temperature, such as 60°C to 90°C, for 3 to 10 minutes, resulting in the formation of a solidified film / layer, which is the electrochromic layer. The solidified film / electrochromic layer is separated from the sacrificial / temporary liner (which is discarded), cut to size (if necessary), and placed on or directly on the first transparent electrode layer of the first substrate. A second transparent electrode of the second substrate is placed on or directly on the other (or opposing / exposed) side of the electrochromic layer to form a stack including the first substrate, the first transparent electrode, the electrochromic layer, the second transparent electrode, and the second substrate. The stack may further include electrical connectors that separately electrically contact the first and second transparent electrodes. The stack (with an optional gasket surrounding at least the outer edge of the electrochromic layer) is subjected to vacuum lamination while simultaneously applying an elevated temperature, such as 110°C to 200°C, for a period of time, such as 10 to 30 minutes. After cooling, the electrochromic device so formed is removed from the vacuum laminated device.

[0119] According to the present invention, there is also provided a compound represented by formula (IIa) as described hereinbefore. 2 Divalent Linking Group and R 3Each of the groups is as described herein above with respect to formula (II) of the electrochromic device of the present invention.

[0120] In some embodiments, R of formula (IIa) 2 is a divalent linear or branched C1-C 10 R of formula (IIa) is selected from alkane linking groups; 3 is fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

[0121] In some further embodiments, R 2 is selected from divalent linear or branched C1-C5 alkane linking groups, R 3 is selected from linear or branched C1-C5 perfluorinated alkyl.

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

[0123] According to the present invention, there is further provided a salt comprising an anion of formula (II) as described hereinbefore. R of the salt according to the present invention comprising an anion of formula (II) 2 Divalent Linking Group and R 3 Each of the groups is as described herein above with respect to formula (II) of the electrochromic device of the present invention.

[0124] In some embodiments, R of formula (II) of the salt according to the present invention 2 is a divalent linear or branched C1-C 10R of formula (II) of the salt of the present invention is selected from alkane linking groups. 3 is fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 The alkyl radicals are selected from perfluorinated alkyl radicals.

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

[0126] According to some embodiments, the salt of the present invention comprises 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 are equivalent, and the salt correspondingly has a neutral charge. In some embodiments, the counter cation of the salt according to the present invention is, for example, but not limited to, as described herein above for the counter cation of the anode component of the present invention with reference to formula (B).

[0127] In some embodiments, the countercation of the salt according to the invention is selected from tetra(linear or branched alkyl)ammonium cations. In some further embodiments, the countercation of the salt according to the invention is selected from tetra(linear or branched C1-C 10 alkyl) ammonium cations.

[0128] The salt of the present invention may have any suitable form, for example, a solid form or may be in the form of an ionic liquid. In some embodiments, the salt of the present invention is present in a liquid mixture further comprising a solvent, such as water and / or an organic solvent. The organic solvent may be selected from any suitable organic solvent, for example, but not limited to, ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitriles, or di(linear or branched C1-C8) acetamide.

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

[0130] Clause 1: (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 opposed to each other and spaced apart from each other; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) a cathode component; (ii) Formula (I) or (II): [ka] an anode component comprising an anode component anion selected from at least one anode component anion represented by In the formula (I), R 1 is selected from divalent linear or branched alkane linking groups; With respect to formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; (iii) an optional electrolyte; and (iv) a polymer matrix; The electrochromic layer comprises: Electrochromic device.

[0131] Clause 2: With respect to formula (I), R 1 Divalent linear or branched C1-C 10 alkane linking groups, With respect to formula (II), R 2 Divalent linear or branched C1-C 10 alkane linking groups; R 3 is fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 selected from perfluorinated alkyls, 2. An electrochromic device as described in clause 1.

[0132] Clause 3: With respect to formula (I), R 1 is selected from divalent linear or branched C1-C5 alkyl; With respect to formula (II), R 2 is selected from divalent linear or branched C1-C5 alkane linking groups, R 3 is selected from linear or branched C1-C5 perfluorinated alkyl; Electrochromic device according to clause 1 or 2.

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

[0134] Clause 5: The electrochromic device of clause 4, wherein each countercation 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: Each counter cation has the following formula (B): Formula (B) [ka] and independently selected from tetra-substituted ammonium cations represented by In the formula, R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl; Electrochromic device according to clause 4 or 5.

[0136] Article 7:R a , R b , R c and R d are each independently linear or branched C1 to C 10 7. The electrochromic device of claim 6, wherein the alkyl group is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0137] Article 8: R a , R b , R c and R d are each independently linear or branched C1 to C 10 8. The electrochromic device of claim 6 or 7, wherein the alkyl is selected from the group consisting of aryl, ... and alkyl.

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

[0139] Clause 10: Each countercation is a tetra (linear or branched C1-C 10 10. The electrochromic device of any one of clauses 4, 5, 6, 7, 8 or 9, wherein the cations are independently selected from the group consisting of alkyl) ammonium cations.

[0140] Clause 11: The cathode component comprises at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): Formula (III) [ka] Formula (IV) [ka] In the formula (III), R 4 and R 5 are each independently linear or branched C1 to C 10 is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl; In the formula (IV), R 6 and R 8 are each independently linear or branched C1 to C 10 is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C1-C 10 alkane linking groups, 11. The electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0141] Clause 12: With respect to formula (III), R 4 and R 5 are each independently selected from linear or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8are each independently selected from linear or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl; R 7 is selected from divalent linear or branched C1-C8 alkane linking groups; 12. An electrochromic device as defined in clause 11.

[0142] Clause 13: The cathode component further comprises a counter anion, each counter anion of the cathode component being BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , and B(phenyl)4 - 13. The electrochromic device according to any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, selected from the group consisting of:

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

[0144] Clause 15: The electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein the polymer matrix comprises a polymer, the polymer comprising 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).

[0145] Clause 16: An article of manufacture comprising the electrochromic device of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, and selected from an energy efficient transparent film, a transparent film for privacy, a mirror, an optical filter or an ophthalmic article.

[0146] Article 17: (i) a cathode component; (ii) Formula (I) or (II): [ka] an anode component comprising an anode component anion selected from at least one anode component anion represented by In the formula (I), R 1 is selected from divalent linear or branched alkane linking groups; In the formula (II), R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; (iii) an optional electrolyte; and (iv) a polymeric thickener; and (v) a solvent; 1. An electrochromic composition comprising:

[0147] Clause 18: With respect to formula (I), R 1 Divalent linear or branched C1-C 10 alkane linking groups, With respect to formula (II), R 2 Divalent linear or branched C1-C 10 alkane linking groups; R 3 Fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 selected from perfluorinated alkyls, 18. The electrochromic composition of claim 17.

[0148] Clause 19: With respect to formula (I), R 1 is selected from divalent linear or branched C1-C5 alkyl; With respect to formula (II), R 2 is selected from divalent linear or branched C1-C5 alkane linking groups, R 3 is selected from linear or branched C1-C5 perfluorinated alkyl; 19. The electrochromic composition according to claim 17 or 18.

[0149] Clause 20: The electrochromic composition of any one of clauses 17, 18 or 19, wherein the anodic component further comprises a counter cation.

[0150] Clause 21: The electrochromic composition of clause 20, wherein each countercation 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] Clause 22: Each counter cation is represented by the following formula (B): Formula (B) [ka] and selected from tetrasubstituted ammonium cations represented by In the formula, R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl; 22. The electrochromic composition according to claim 20 or 21.

[0152] Article 23:R a , R b , R c and R d are each independently linear or branched C1 to C 10 23. The electrochromic composition of claim 22, wherein the alkyl group is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0153] Article 24:R a , R b , R c and R d are each independently linear or branched C1 to C 10 24. The electrochromic composition of claim 22 or 23, wherein the alkyl is selected from the group consisting of aryl, aryl, aryl and alkyl.

[0154] Clause 25: The electrochromic composition of any one of clauses 17, 18, 19, 20, 21, 22, 23 or 24, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0155] Clause 26: Each counter cation is a tetra (linear or branched C1-C 10 26. The electrochromic composition of any one of clauses 17, 18, 19, 20, 21, 22, 23, 24 or 25, wherein the cation is independently selected from the group consisting of alkyl)ammonium cations.

[0156] Clause 27: The cathode component comprises at least one of a 1,1'-disubstituted-4,4'-dipyridinium cation represented by the following formula (III) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1'-substituted-4,4'-dipyridinium) cation represented by the following formula (VI): Formula (III) [ka] Formula (IV) [ka] In the formula (III), R 4 and R 5 are each independently linear or branched C1 to C 10 is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl; In the formula (IV), R 6 and R 8 are each independently linear or branched C1 to C 10 is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cyloalkyl, unsubstituted aryl, and substituted aryl; R 7 is a divalent linear or branched C1-C 10 alkane linking groups, 27. The electrochromic composition according to any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25 or 26.

[0157] Clause 28: With respect to formula (III), R 4 and R 5 are each independently selected from linear or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl; With respect to formula (IV), R 6 and R 8are each independently selected from linear or branched C1-C4 alkyl, unsubstituted phenyl, and substituted phenyl; R 7 is selected from divalent linear or branched C1-C8 alkane linking groups; 28. The electrochromic composition of claim 27.

[0158] Clause 29: The cathode component further comprises a counter anion, each counter anion of the cathode component being BF4 - , PF6 - , ClO4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - , and B(phenyl)4 - 30. The electrochromic composition of any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28, selected from the group consisting of:

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

[0160] Clause 31: The electrochromic composition of any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30, wherein the polymeric thickener comprises a polymer, the polymer comprising 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).

[0161] Clause 32: The electrochromic composition of any one of clauses 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 or 31, wherein the solvent comprises at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid ester of polyethylene glycol, sulfolane, alpha, omega-(C2-C8) dinitrile, or di(linear or branched C1-C8) acetamide.

[0162] Clause 33: a compound represented by the following formula (IIa): [ka] A compound represented by (In the formula, R 2 is selected from divalent linear or branched alkane linking groups; R 3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

[0163] Article 34:R 2 Divalent linear or branched C1-C 10 alkane linking groups; R 3Fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 34. The compound according to claim 33, selected from perfluorinated alkyls.

[0164] Article 35:R 2 is selected from divalent linear or branched C1-C5 alkane linking groups, R 3 is selected from linear or branched C1-C5 perfluorinated alkyl.

[0165] Clause 36: A compound represented by the following formula (II): [ka] A salt containing an anion represented by (In the formula, R 1 is selected from divalent linear or branched alkane linking groups; R 2 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

[0166] Clause 37: For the anion represented by formula (II), R 2 Divalent linear or branched C1-C 10 alkane linking groups; R 3 Fluorine, linear or branched C1-C 10 Fluorinated alkyl, or linear or branched C1-C 10 37. The salt according to claim 36, selected from perfluorinated alkyls.

[0167] Clause 38: For the anion represented by formula (II), R 2 is selected from divalent linear or branched C1-C5 alkane linking groups, R 3 38. The salt according to clause 36 or 37, wherein is selected from linear or branched C1-C5 perfluorinated alkyl.

[0168] Clause 39: The salt according to any one of clauses 36, 37 or 38, wherein the salt further comprises a counter cation.

[0169] Clause 40: The salt of clause 39, wherein each countercation 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] Clause 41: Each counter cation is represented by the following formula (B): Formula (B) [ka] and selected from tetrasubstituted ammonium cations represented by In the formula, R a , R b , R c and R d are each independently selected from linear or branched alkyl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substituted aryl; A salt as defined in clause 39 or 40.

[0171] Article 42:R a , R b , R c and R d are each independently linear or branched C1 to C 10 42. The salt according to clause 41, wherein the alkyl is selected from alkyl, unsubstituted C3-C7 cycloalkyl, substituted C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl.

[0172] Article 43:R a , R b , R c and R d are each independently linear or branched C1 to C 10 43. The salt according to clause 41 or 42, wherein the alkyl is selected from the group consisting of aryl, ... and alkyl.

[0173] Clause 44: The salt of any one of clauses 36, 37, 38, 39, 40, 41, 42 or 43, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

[0174] Clause 45: Each countercation is a tetra (linear or branched C1-C 10 45. The salt according to any one of clauses 36, 37, 38, 39, 40, 41, 42, 43 or 44, wherein the cations are independently selected from the group consisting of alkyl, aryl, arylalkyl ...

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

[0176] example Part 1 of the following examples describes the synthesis of anode component anions and salts of anode components according to the invention. Part 2 describes the preparation of electrochromic devices according to the invention. Part 3 describes the evaluation of the electrochromic devices of Part 2.

[0177] Part 1 Synthesis Example 1 Referring to Scheme (1) below, a non-limiting illustration of the preparation of an anode component anion according to the present invention represented by formula (I) is provided, wherein R 1 is a divalent n-propane linking group.

[0178] To an oven-dried 500 ml three-neck round-bottom flask with magnetic stirring was added 200 ml of dimethylformamide (DMF) and 10 g of (1) phenothiazine (50.2 mmol). The solution was stirred for 1 hour while purging with nitrogen. To the reaction mixture was added 2.4 g of 60% NaH (60 mmol). The solution was observed to turn deep red in color as gas bubbles were generated therefrom. After 1 hour of continuous mixing under nitrogen, the generation of gas bubbles was observed to cease. Under a nitrogen sweep, 6.6 g of (2) 1,3-propane sultone (55.2 mmol) dissolved in 10 g of dry 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 left stirring 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 a vacuum, after which an oily material remained in the flask. 50 ml of ethyl acetate was added to the oily material, forming a precipitate which was collected by vacuum filtration. The precipitate was washed with cold ethyl acetate and dried overnight under vacuum at 60° C. to give the desired product (3) sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate as an off-white solid. Scheme (1) [ka]

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

[0181] (3) Sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was prepared according to Synthesis Example 1. 1 gram (0.0029 mol) of (3) Sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate was finely ground in a mortar and pestle and then placed in a 100 ml round bottom flask equipped with a magnetic stir bar and a reflux condenser with N2 sweep / blanket. 20 ml 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 it was observed that solid sodium salt (3) was present. (4) Cyanuric acid chloride (540 mg, 0.0029 mol, 1 equiv.) was added with vigorous stirring under N2. The mixture was refluxed in an oil bath (approximately 80° C.) for 24 hours. The color of the solution turned orange and a fine precipitate formed. Large chunks of the initial Na salt (3) were no longer observable. Thin layer chromatography (TLC) showed the presence of a single reaction product that turned pink upon exposure to shortwave (316 nm) UV in air, proving the formation of (5) 3-(10H-phenothiazin-10-yl)-propane-1-sulfonyl chloride. The product (5) was fairly mobile in 50:50 EtOAc / hexanes. The reaction mixture was cooled to room temperature and filtered through a thin layer of alumina. The solvent was removed under vacuum 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 further 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 three-neck flask equipped with a reflux condenser, a magnetic stir bar, and a fritted Schlenk funnel. A nitrogen source was attached to the condenser and Schlenk funnel and secured with plastic clips. The vessel was flushed for 15 s using a strong nitrogen flux, and a septum was placed on the remaining neck. An amount of 100 ml of anhydrous MeCN was added through the septum using a syringe. The mixture was stirred vigorously for 20 min, resulting in a white cloudy dispersion. To the crude (5) 3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride (9.84 g, 0.029 mol) (filtrate from previous step), 50 ml of dry MeCN was added under nitrogen flux and the resulting solution was transferred to a fritted Schlenk funnel. The Schlenk funnel was purged with nitrogen and stoppered with a clip. The solution of MeCN and (5) 3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride was added dropwise to the three-neck flask at room temperature over 1 h. The contents of the three-neck flask were refluxed for 24 h. The formation of a bulky precipitate was observed. The precipitate was filtered off and the resulting solution was concentrated under vacuum. The residue was recrystallized from water to give the product (7) potassium 3-(10H-phenothiazin-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonamide in the form of brown needles. Scheme (2) [ka]

[0183] Part 2 An electrochromic device according to the present invention was prepared according to the following procedure: An initial solution was prepared with magnetic stirring of propylene carbonate (7 g); ethylene carbonate (3 g); 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonimide (EMIM-TFSI) (1 g); potassium 3-(10H-phenothiazin-10-yl)-N-triflylpropane-1-sulfonamide (PTTK) (100 mg); and 1,1'-diethyl-4,4'-bipyridinium bis(trifluoromethane)sulfonimide (diethyl viologen TFSI) (100 mg). 3.5 g of polyacrylonitrile was added to the initial solution, followed by homogenization to form a thick slurry. A liquid film of the thick slurry was formed on a sacrificial polyethylene terephthalate (PET) liner to a thickness of 400 micrometers (um) using a doctor blade. The liquid film was heated to 70°C for 10 minutes to form a solidified film / layer which was the electrochromic layer. The solidified film / electrochromic layer was separated from the sacrificial / temporary liner, cut to size (2" x 3", 5.08 cm x 7.62 cm) and placed on a Fluorine-doped Tin Oxide (FTO) glass electrode (3" x 4", 7.62 cm x 10.16 cm) that already had copper tape wrapped around the insulating polyimide covered edges. A pre-fabricated thermoplastic gasket 0.5" (1.27 cm) wide and 400 microns thick was added to surround the active area. A second Fluorine-doped Tin Oxide (FTO) glass was placed on top of 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 so-formed electrochromic device was removed from the vacuum laminated device.

[0184] Part 3 Plots of % transmission vs. wavelength (nm) for the Part 2 electrochromic device in the light / deactivated and dark / activated states (at room temperature in each case) are shown in Figure 2 of the drawings. With reference to Figure 2, an electrochromic device according to the present invention provides a significant and desirable level of dimming (i.e., reduced visible light transmission) when activated compared to its light / deactivated state. In Figure 2, the Part 2 electrochromic device is labeled "PTTK-Ethyl Viologen Device." With further reference to Figure 2, the plot of % transmission vs. wavelength for the light / deactivated state is labeled "PTTK-EV Light" and the plot of % transmission vs. wavelength for the dark / activated state is labeled "PTTK-EV Dark."

[0185] The invention has been described with reference to specific details of particular embodiments thereof, and it is not intended that such details be considered limitations on the scope of the invention, except to the extent that they are included in the appended claims.

Claims

1. (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 opposed to each other and spaced apart from each other; (c) an electrochromic layer interposed between the first transparent conductive electrode layer and the second transparent conductive electrode layer, (i) a cathode component; and (ii) a compound represented by the following formula (I) or (II): 【Chemistry 1】 an anode component comprising at least one anode component anion selected from the group consisting of In the formula (I), R １ is selected from divalent linear or branched alkane linking groups; For formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; (iii) an optional electrolyte; and (iv) a polymer matrix; The electrochromic layer comprises: Electrochromic device.

2. For formula (I), R １ is a divalent linear or branched C １ ~C １０ alkane linking groups, For formula (II), R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl, or linear or branched C １ ~C １０ selected from perfluorinated alkyls, The electrochromic device of claim 1 .

3. For formula (I), R １ is a divalent linear or branched C １ ~C ５ alkyl, For formula (II), R ２ is a divalent linear or branched C １ ~C ５ alkane linking groups; R ３ is linear or branched C １ ~C ５ selected from perfluorinated alkyls, 3. The electrochromic device of claim 2.

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

5. 5. The electrochromic device of claim 4, wherein each countercation is independently selected from tetra(linear or branched alkyl)ammonium cations.

6. Each counter cation is a tetra (linear or branched C １ ~C １０ 6. The electrochromic device of claim 5, wherein the cations are independently selected from the group consisting of alkyl) ammonium cations.

7. The cathode component comprises at least one of a 1,1′-disubstituted-4,4′-dipyridinium cation represented by the following formula (III) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented by the following formula (VI): 【Chemistry 2】 In the formula (III), R ４ and R ５ are each independently a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; In the formula (IV), R ６ and R ８ are each independently a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R ７ is a divalent linear or branched C １ ~C １０ alkane linking groups, The electrochromic device of claim 1 .

8. For formula (III), R ４ and R ５ each independently represents a linear or branched C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; For formula (IV), R ６ and R ８ each independently represents a linear or branched C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; R ７ is a divalent linear or branched C １ ~C ８ alkane linking groups, 8. The electrochromic device of claim 7.

9. The cathode component further comprises a counter anion, each counter anion of the cathode component being BF ４ － , P.F. ６ － , ClO ４ － , C.F. ３ SO ３ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and B(phenyl) ４ － 8. The electrochromic device of claim 7, selected from the group consisting of:

10. The electrolyte is present, At least one electrolyte anion, each electrolyte anion being bis(perfluoro(linear or branched C １ ~C ６ at least one electrolyte anion independently selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation being 1-(linear or branched C １ ~C ６ Alkyl)-3-(linear or branched C １ ~C ６ alkyl)imidazolium, 1-(linear or branched C １ ~C ６ Alkyl)-1-(linear or branched C １ ~C ６ Alkyl) piperidinium, tetra(linear or branched C １ ~C ６ alkyl) ammonium, or tri(C ５ ~C ８ Cycloalkyl)-(linear or branched C １ ~C ６ at least one electrolyte cation independently selected from the group consisting of ammonium, ammonium cations, The electrochromic device of claim 1 , comprising:

11. The polymer matrix comprises a polymer, the polymer being selected from the group consisting of poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C １ ~C ６ alkylene)) or poly((linear or branched C １ ~C ８ 10. The electrochromic device of claim 1 comprising at least one of:

12. (i) a cathode component; and (ii) a compound represented by the following formula (I) or (II): 【Chemistry 3】 an anode component comprising at least one anode component anion selected from the group consisting of In the formula (I), R １ is selected from divalent linear or branched alkane linking groups; In the formula (II), R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl; (iii) an optional electrolyte; and (iv) a polymeric thickener; and (v) a solvent; 1. An electrochromic composition comprising:

13. For formula (I), R １ is a divalent linear or branched C １ ~C １０ alkane linking groups, For formula (II), R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl, or linear or branched C １ ~C １０ selected from perfluorinated alkyls, The electrochromic composition of claim 12.

14. For formula (I), R １ is a divalent linear or branched C １ ~C ５ alkyl, For formula (II), R ２ is a divalent linear or branched C １ ~C ５ alkane linking groups; R ３ is linear or branched C １ ~C ５ selected from perfluorinated alkyls, The electrochromic composition of claim 13.

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

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

17. Each counter cation is a tetra (linear or branched C １ ~C １０ 17. The electrochromic composition of claim 16, wherein the cations are independently selected from the group consisting of alkyl) ammonium cations.

18. The cathode component comprises at least one of a 1,1′-disubstituted-4,4′-dipyridinium cation represented by the following formula (III) or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented by the following formula (VI): Formula (III) 【Chemistry 4】 Formula (IV) 【Chemistry 5】 In the formula (III), R ４ and R ５ are each independently a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; In the formula (IV), R ６ and R ８ are each independently a linear or branched C １ ~C １０ Alkyl, unsubstituted C ３ ~C ７ Cycloalkyl, substituted C ３ ~C ７ is selected from cycloalkyl, unsubstituted aryl, and substituted aryl; R ７ is a divalent linear or branched C １ ~C １０ alkane linking groups, The electrochromic composition of claim 12.

19. For formula (III), R ４ and R ５ each independently represents a linear or branched C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; For formula (IV), R ６ and R ８ each independently represents a linear or branched C １ ~C ４ selected from alkyl, unsubstituted phenyl, and substituted phenyl; R ７ is a divalent linear or branched C １ ~C ８ alkane linking groups, 20. The electrochromic composition of claim 18.

20. The cathode component further comprises a counter anion, each counter anion of the cathode component being BF ４ － , P.F. ６ － , ClO ４ － , C.F. ３ SO ３ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and B(phenyl) ４ － 20. The electrochromic composition of claim 18 selected from the group consisting of:

21. The electrolyte is present, At least one electrolyte anion, each electrolyte anion being bis(perfluoro(linear or branched C １ ~C ６ at least one electrolyte anion independently selected from the group consisting of alkylsulfonyl)imides; At least one electrolyte cation, each electrolyte cation being 1-(linear or branched C １ ~C ６ Alkyl)-3-(linear or branched C １ ~C ６ alkyl)imidazolium, 1-(linear or branched C １ ~C ６ Alkyl)-1-(linear or branched C １ ~C ６ Alkyl) piperidinium, tetra(linear or branched C １ ~C ６ alkyl) ammonium, or tri(C ５ ~C ８ Cycloalkyl)-(linear or branched C １ ~C ６ at least one electrolyte cation independently selected from the group consisting of ammonium, ammonium cations, The electrochromic composition of claim 12 comprising:

22. The polymeric thickener comprises a polymer, the polymer being selected from the group consisting of poly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linear or branched C １ ~C ６ alkylene)) or poly((linear or branched C １ ~C ８ 13. The electrochromic composition of claim 12 comprising at least one of:

23. The solvent may be ethylene carbonate, propylene carbonate, gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters of polyethylene glycol, sulfolane, alpha, omega-(C ２ ~C ８ ) dinitrile, or di(linear or branched C １ ~C ８ 13. The electrochromic composition of claim 12, comprising at least one of:

24. The following formula (IIa): 【Chemistry 6】 A compound represented by (In the formula, R ２ is selected from divalent linear or branched alkane linking groups; R ３ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

25. R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl, or linear or branched C １ ~C １０ 25. The compound of claim 24 selected from perfluorinated alkyls.

26. R ２ is a divalent linear or branched C １ ~C ５ alkane linking groups; R ３ is linear or branched C １ ~C ５ 26. The compound of claim 25 selected from perfluorinated alkyls.

27. The following formula (II): 【Chemistry 7】 A salt containing an anion represented by (In the formula, R １ is selected from divalent linear or branched alkane linking groups; R ２ is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl.

28. For the anion represented by formula (II), R ２ is a divalent linear or branched C １ ~C １０ alkane linking groups; R ３ is fluorine, linear or branched C １ ~C １０ Fluorinated alkyl, or linear or branched C １ ~C １０ 28. The salt of claim 27 selected from perfluorinated alkyls.

29. For the anion represented by formula (II), R ２ is a divalent linear or branched C １ ~C ５ alkane linking groups; R ３ is linear or branched C １ ~C ５ 29. The salt of claim 28 selected from perfluorinated alkyls.

30. 28. The salt of claim 27 further comprising a counter cation.

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

32. Each counter cation is a tetra (linear or branched C １ ~C １０ 32. The salt of claim 31 , wherein the cations are independently selected from the group consisting of alkyl, aryl ...

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