High-transparency electrochromic polymer

Abstract

To provide a new type of electrochromic polymer and a device using this polymer. [Solution] Electrochromic polymers are JPEG2026057544000090.jpg21170 (In the formula, MCL represents the meta-conjugated linker, and Ac represents the aromatic moiety) The disclosed electrochromic polymer has absorption initiation below 420 nm in the neutral state and absorption in the visible and / or near-infrared wavelengths in the oxidized state. Therefore, when used in an electrochromic device, the disclosed electrochromic polymer exhibits high transparency and high optical contrast.

Description

[Technical Field]

[0001] Cross-reference of related applications This application is a continuation of non-provisional application No. 18 / 889,042 filed on 18 September 2024, a continuation in part of non-provisional application No. 18 / 395,603 filed on 24 December 2023, a continuation in part of non-provisional application No. 18 / 093,287 filed on 4 January 2023, a continuation in part of non-provisional application No. 17 / 748,383 filed on 19 May 2022 (currently U.S. Patent No. 11,874,578 published on 16 January 2024), and a continuation in part of non-provisional application No. 17 / 668,300 filed on 9 February 2022 (currently U.S. Patent No. 11,879,098 published on 23 January 2024). All the contents of the above-mentioned applications are incorporated herein by reference in their entirety.

[0002] This disclosure relates to a novel type of electrochromic polymer comprising a meta-conjugated linker and an aromatic moiety, which exhibits high transparency in the visible light region in a neutral state. When the film of this polymer is oxidized, it exhibits high absorption in the visible and near-infrared regions, and is therefore colored. Devices incorporating such conjugated electrochromic polymer films having high optical contrast and high transmittance are also disclosed. [Background technology]

[0003] Electrochromic elements allow for the adjustment of light transmittance and control of solar heat acquisition. Compared to inorganic electrochromic elements manufactured through vacuum sputtering processes, polymer-based electrochromic windows can be manufactured through roll-to-roll coating and lamination. This thus results in low-cost production and manufacturing flexibility. Polymer-based electrochromic elements are typically manufactured using sputtering. 2It is composed of conjugated electrochromic polymers (ECPs) characterized by a fully conjugated polymer backbone made from hybrid carbon. Conventionally, ECPs typically have strong absorbance in the visible light region and are therefore colored in their neutral state. When they are oxidized, their absorption shifts to the near-infrared (near-IR) region, and they become transparent in the visible light region. However, oxidized polymers have weak absorption in the visible light region, resulting in residual color. The problem becomes more serious with thicker polymer films. As a result, it negatively affects the optical contrast of the polymer. Furthermore, it limits the highest light transmittance that conjugated electrochromic polymers can achieve. In addition, conventional ECPs in the neutral state block visible light and transmit near-infrared light through the film, while in the transparent state, they transmit visible light and block near-infrared light. This combination is not effective for heat management and control of solar heat gain (SHG). SHG represents the way in which radiation from the sun is converted into heat through window products. [Overview of the project] [Problems that the invention aims to solve]

[0004] This disclosure relates to a new type of electrochromic polymer and a device using this polymer. [Means for solving the problem]

[0005] This application is, [ka] Provided is a new type of electrochromic polymer containing the formula. In this formula, MCL represents a meta-conjugated linker, and Ac represents an aromatic moiety. Here, y is an integer greater than or equal to 0, n and x are integers greater than 1; a, b, c, d,..., m, a', b', c', d',..., m' are the ratios of the monomers in the electrochromic polymer; the sum of a, b, c, d,..., m, a', b', c', d',..., m' is equal to 1, 0 < each of a and b < 1, 0 ≤ each of c, d,..., m, a', b', c', d',... and m' < 1; the sum of a', b', c', d',..., m' is less than or equal to the sum of a, b, c, d,..., m.

[0006] MCL includes at least one of an aromatic structure or a condensed aromatic structure, or a combination thereof. In some embodiments, MCL is benzene, or naphthalene, or a condensed benzene structure, or a heterocyclic ring, or a condensed ring structure, or a benzene-condensed ring structure, or at least one of a first benzene condensed with a ring structure condensed with a second benzene, or a combination of these structures. In some embodiments, each of MCL (MCL1, MCL2, MCL3, MCL4,..., and MCL x ) and the corresponding meta-position includes one of the following formulas.

[0007]

Chemical formula

[0008]

Chemical formula

[0009]

Chemical formula

[0010]

Chemical formula

[0011] [Chemical]

[0012] [Chemical]

[0013] [Chemical]

[0014] Ac1, Ac2, Ac3, Ac4, …, Ac y each of which is [Chemical] selected from one of a benzene-based unit, a naphthalene-based unit, a fluorene-based unit, a pyrrole-based unit, or a thiophene-based unit having the formula. In the above formula, X is S, Se, N, C, or O, and each of the wavy lines represents a position connected to an adjacent aromatic structure of MCL or Ac.

[0015] When each of c, d, …, m, a’, b’, c’, d’, …, m’ is equal to 0, for each MCL, at least one of R1 to R 12 is C1 to C 30 alkyl, C2 to C 30 alkenyl, C2 to C 30 alkynyl, C2 to C 30 alkylcarbonyl, C1 to C 30 alkoxy, C3 to C 30 alkoxyalkyl, C2 to C 30 alkoxycarbonyl, C4 to C 30 alkoxycarbonylalkyl, C1 to C 30 alkylthio, C1 to C 30 aminylcarbonyl, C4 to C 30 aminylalkyl, C1 to C 30 alkylaminyl, C1 to C 30 alkylsulfonyl, C3 to C 30Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkylalkyloxy, C1-C 12 Heterocyclyl, C1-C 12 Heterocyclyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3-C 30 Heteroarylalkyl, C2-C 30 Polyethylene glycol, or C3-C 30 selected from one of polyethylene glycol ethers.

[0016] When 0 < at least one of c, d,..., m, a', b', c', d',... and m' < 1, in at least one Ac, at least one of R 21 ~R 36 and in at least one MLC, at least one of R1~R 12 is C1-C 30 alkyl, C2-C 30 alkenyl, C2-C 30 alkynyl, C2-C 30 alkylcarbonyl, C1-C 30 alkoxy, C3-C 30 alkoxyalkyl, C2-C 30 alkoxycarbonyl, C4-C 30 alkoxycarbonylalkyl, C1-C 30 alkylthio, C1-C 30 aminylcarbonyl, C4-C 30 aminylalkyl, C1-C 30Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of the polyethylene glycol ethers, R 21 ~R 36 Each of the remaining ones and R1~R 12 Each of the remaining ones is hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkylalkyloxy, C1-C 12 Heterocyclyl, C1-C 12 Heterocyclyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3-C 30 Heteroarylalkyl, C2-C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of polyethylene glycol ethers.

[0017] The disclosed new type of electrochromic polymer has an absorption onset at 420 nm or less in the neutral state and has absorption at visible and / or near-infrared wavelengths in the oxidized state. In some embodiments, the disclosed new type of electrochromic polymer is colorless in the neutral state of the electrochromic polymer. In some embodiments, the disclosed new type of electrochromic polymer has at least one absorption peak between 390 and 460 nm including both ends in the oxidized state.

[0018] In some embodiments, MCL1 has the following formula.

Chemical formula

[0019] In some embodiments, 0 < each of a, b, c, a', b', and c' < 1, and for the disclosed new type of electrochromic polymer, each of d, …, m, d', …, m' is equal to 0. In some embodiments, 0 < each of a, b, c, a' < 1, and for the disclosed new type of electrochromic polymer, each of d, …, m, b', c', d', …, m' is equal to 0.

[0020] In some embodiments, each of Ac1, Ac2, Ac3, Ac4, …, Ac y contains a thiophene-based unit, and the thiophene-based unit has the following formula:

Chemical formula

[0021] In some embodiments, the novel type of electrochromic polymer disclosed includes the following formula:

[0022] [ka]

[0023] [ka]

[0024] (In the formula, n is an integer greater than 1, the sum of α, β, γ, α', β', γ' is equal to 1, 0 < α, β, γ, α', β', and γ' each < 1, and the sum of α', β', γ' is less than or equal to the sum of α, β, γ)

[0025] In another embodiment, a new type of electrochromic element is provided.

[0026] The disclosed novel type of electrochromic element comprises a first insulating substrate, a first conductive layer disposed on the first insulating substrate, an electrochromic layer disposed on the first conductive layer, an electrolyte layer disposed on the electrochromic layer, a second conductive layer disposed on the electrolyte layer, and a second insulating substrate disposed on the second conductive layer, wherein the electrochromic layer comprises the novel type of electrochromic polymer described above.

[0027] In some embodiments, the electrochromic layer has a transmittance of 70% to 99.9% at a wavelength of 416 nm in the neutral state of the electrochromic layer. For example, the thickness of the electrochromic layer has a transmittance of 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 99.9%, or any two of the above values. In some embodiments, the electrochromic layer is colorless in the neutral state of the electrochromic layer. In some embodiments, the electrochromic element has a transmittance of 50% or more at a wavelength of 416 nm in the bleached state (white state) of the element. For example, an electrochromic element may have a transmittance of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or any two of the above values ​​in a bleached state. In some embodiments, the electrochromic layer has a transmittance of 95.1% to 0.1% at a wavelength of 416 nm in an oxidized state. For example, an oxidized electrochromic layer has transmittances of 95.1%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1%, or any two of the above values, at a wavelength of 416 nm. In some embodiments, the electrochromic layer has an optical contrast of 50% or more. For example, the electrochromic layer may have an optical contrast of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or any two of the above values. In some embodiments, the electrochromic layer has at least one absorption peak between 390 and 460 nm, including both ends, in the oxidized state. In some embodiments, the electrochromic element has an optical contrast of 50% or more.For example, an electrochromic element may have an optical contrast of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or any two of the above values.

[0028] Features of various embodiments of this technology are described in detail in the appended claims. A better understanding of the features and advantages of this technology will be obtained by referring to the following detailed description illustrating exemplary embodiments in which the principles of the present invention are utilized, and to the accompanying drawings below. For the purpose of illustrating the present invention, the drawings illustrate aspects of one or more embodiments of the present invention. However, it should be understood that the present invention is not limited to the exact apparatus and means shown in the drawings. [Brief explanation of the drawing]

[0029] [Figure 1(A)] This figure illustrates a different color change mechanism of the ECP of this disclosure compared to a conventional ECP (Figure 1(B)). [Figure 1(B)] This diagram illustrates the color change mechanism of conventional ECP. [Figure 2] This figure shows the CV data of an exemplary solid-state device using Example ECP-1 according to one embodiment. [Figure 3] This is a diagram illustrating the switching kinetics of a typical solid-state device using Example ECP-1 at 545 nm according to one embodiment. [Figure 4] This figure shows the absorbance spectra of an exemplary ECP-1 thin film at different voltages according to one embodiment. [Figure 5] This figure shows the CV data of an exemplary solid-state element using another embodiment, ECP-2, according to one of the embodiments. [Figure 6] This is a diagram illustrating the switching kinetics of an exemplary solid-state device using Example ECP-2 at 550 nm according to one embodiment. [Figure 7]This figure shows the absorbance spectra of an exemplary ECP-2 thin film at different voltages according to one embodiment. [Figure 8(A)] This figure shows the calculated neutral-state UV-Vis spectra of disclosed metaconjugated polymers having three representative MCLs according to several embodiments. [Figure 8(B)] This figure shows the calculated UV-Vis spectra of the oxidized states of three representative metaconjugated polymers having MCLs according to several embodiments. [Figure 9(A)] This figure shows the absorption spectroscopy and electrochemistry of a 300 nm thick CBZ-blend polymer transitioning from a neutral to an oxidized state in several embodiments. From the bottom line to the top line, the potentials are 0.6V, 0.65V, 0.7V, 0.75V, 0.8V, 0.85V, 0.9V, 0.95V, and 1.0V (vs. Ag / AgCl), respectively. [Figure 9(B)] This figure shows Beer-Lambert plots of the neutral state (dashed line) and oxidized state (solid line) of CBZ-blends at 550 nm. [Figure 9(C)] This figure shows the transmittance at 550 nm of CBZ-blends in neutral and oxidized states as a function of film thickness, according to several embodiments. Experimental results are shown as points, while calculated results are shown as solid and dashed lines. [Figure 9(D)] This figure shows the transmittance of CBZ-blends in both neutral and oxidized states of EC layers of different thicknesses according to several embodiments. [Figure 9(E)] This figure shows the transmittance of CBZ-blends in both the neutral (bleached) (white) and oxidized states of the EC layer under 10,000 cycles, according to several embodiments. [Figure 10] This is a cross-sectional view of an electrochromic element according to one exemplary embodiment of the present disclosure. [Figure 11] This figure shows the absorbance spectra of an exemplary PC-1 solid-state device according to one embodiment in a neutral state (-0.4V, solid line) and an oxidized state (1.75V, dashed line). [Figure 12] This figure shows the CV data of an exemplary solid-state element using another embodiment PC-1 according to one embodiment. [Figure 13] This figure shows the switching kinetics of an exemplary solid-state device at 416 nm using Example PC-1 according to one embodiment. [Figure 14] This figure shows the absorbance spectra of an exemplary PC-2 solid-state element according to one embodiment in a neutral state (-0.4V, solid line) and an oxidized state (1.08V, dashed line). [Figure 15] This figure shows the CV data of an exemplary solid-state element using another embodiment PC-2 according to one embodiment. [Figure 16] This figure shows the switching kinetics of an exemplary solid-state device at 416 nm using Example PC-2 according to one embodiment. [Modes for carrying out the invention]

[0030] The following description includes certain details in order to provide a complete understanding of the various embodiments of the present invention. However, those skilled in the art will understand that the present invention can be carried out without these details. Furthermore, although various embodiments of the present invention are disclosed herein, many modifications and alterations can be made within the scope of the invention in accordance with the general knowledge common to those skilled in the art. Such modifications include the substitution of equivalents known to any aspect of the present invention in order to achieve substantially the same results in substantially the same manner.

[0031] Unless otherwise specified in the context, the word “comprise,” and its variations such as “comprises” and “comprising,” should be interpreted throughout this specification and the claims as having an open and inclusive meaning, i.e., “includes, but is not limited to.” Numerical range descriptions throughout the specification are intended to function as abbreviations for individually referring to each individual value within the range that includes the value defining the range, and each individual value is incorporated into the specification as it is individually described herein. Furthermore, the singular forms “a,” “an,” and “the” include multiple referents unless explicitly indicated in the context.

[0032] Throughout this specification, any reference to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in relation to an embodiment is included in at least one embodiment of the present invention. Therefore, the appearance of the phrase “in one embodiment” or “in one embodiment” in various places throughout this specification does not necessarily refer to the same embodiment, but could be several examples. Furthermore, particular features, structures, or characteristics may be combined in any preferred manner in one or more embodiments.

[0033] This disclosure relates to a novel type of electrochromic polymer. The electrochromic polymers disclosed herein consist of a polymer backbone comprising one or more metaconjugated linkers (MCLs) and one or more aromatic moieties (Ars). Each of the one or more MCLs is partially conjugated with one or more Ars at the meta position of the one or more MCLs to form the polymer backbone of the electrochromic polymer. In some embodiments, the electrochromic polymers disclosed herein consist of repeating units comprising one or more MCLs and one or more Ars, and the metaconjugation is introduced along the polymer backbone through the use of MCLs. In some embodiments, the electrochromic polymer is an anodic colored electrochromic polymer (AC-ECP), which becomes colored when the polymer is oxidized.

[0034] As shown in Figure 1, conventional conjugated ECP (Figure 1(B)) is fully conjugated and has strong absorbance in the visible light region, and therefore is colored in its neutral state, while when oxidized (oxidized state), its absorption shifts to the near-infrared (near-IR) region and it becomes transmissive. However, the oxidized polymer still has weak absorption in the visible light region, leading to residual color. On the other hand, as illustrated in one example disclosed in the ECP of Figure 1(A), the ECP shows virtually no absorption beyond 450 nm in its neutral state, and in its oxidized state, it has several absorption peaks in the visible light and near-infrared ranges, showing coloration in the visible light range and near-infrared absorption.

[0035] The electrochromic polymers of this disclosure can synchronize the transmission or blocking of visible light and near-infrared (near-IR) light, which is very useful in one embodiment in an electrochromic window for managing solar heat acquisition. The electrochromic polymers of this disclosure are transparent in a neutral state and colored and IR absorbent in an oxidized state, and this property is highly desirable for achieving high optical contrast, high transmittance, and synergistic solar heat acquisition.

[0036] The electrochromic polymers disclosed herein are transparent in the visible light region in a neutral state and colored in an oxidized state. For example, the electrochromic polymers disclosed herein may have a transmittance of at least 60% in the visible light region (e.g., 450 to 750 nm) in a neutral state. In some embodiments, the electrochromic polymers disclosed herein may have a transmittance of at least 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 98%, or higher in the 450 to 750 nm range in a neutral state. In some embodiments, the electrochromic polymers disclosed herein are transparent in the visible light region in a neutral state. In an oxidized state, the electrochromic polymers disclosed herein have absorption in the visible light region (e.g., about 360 to 750 nm) and the near-infrared region (e.g., about 750 to 1600 nanometers), thereby coloring and being near-infrared absorbent.

[0037] The electrochromic polymers of this disclosure have UV absorption and an energy band gap. The energy band gap is the energy difference between the valence band and the conduction band of an electron. It is the minimum change in energy required to excite an electron to a state in the conduction band that can participate in conduction. Absorption onset (λ c ) is a wavelength higher than the wavelength at which the polymer does not have photon absorption. The energy band gap can be calculated as 1240 / absorption onset wavelength. In some embodiments, the electrochromic polymers disclosed herein have absorption onset at 450 nm or less in a neutral state. In some embodiments, the electrochromic polymers disclosed herein have absorption onset at 440 nm, 430 nm, 420 nm, 410 nm, 405 nm, or 400 nm or less in a neutral state. In some embodiments, the absorption maximum (λ max The wavelength at which the polymer has its strongest photon absorption is less than 420 nm in a neutral state. In some embodiments, the absorption maximum is less than 410 nm, 405 nm, or 400 nm in a neutral state. In some embodiments, the electrochromic polymer of the Disclosure has an energy band gap of 2.8 eV or greater and less than 4.0 eV in a neutral state. In some embodiments, the electrochromic polymer of the Disclosure has an energy band gap of 2.9, 3.0, or 3.1 eV or greater and less than 4.0 eV in a neutral state. In some embodiments, the electrochromic polymers of this disclosure are colorless in a neutral state (e.g., no absorbance at 400-750 nm, 410-750 nm, or 420-750 nm) or yellow (e.g., tailing absorption at 400-500 nm, 410-500 nm, 420-500 nm, 400-480 nm, 410-480 nm, 420-480 nm, 400-450 nm, 410-450 nm, or 420-450 nm), colored in an oxidized state, visible, and near-infrared (near-IR) absorbent. The oxidized electrochromic polymers exhibit 10 in the visible and / or near-infrared (near-IR) region. 4 cm -1It has a higher absorption coefficient and therefore discolors in an oxidized state.

[0038] Due to substantial absorbance in the visible light range in the neutral state and high absorbance in the visible light range in the oxidized state, the electrochromic polymers of this disclosure demonstrate higher optical contrast and higher light transmittance compared to conventional ECPs. Despite the high band gap, the electrochromic polymers of this disclosure have a relatively low oxidation potential in the range of 0.1 to 1.5 V (inclusive) with respect to the Ag / AgCl electrode in some embodiments. In some embodiments, the electrochromic polymers of this disclosure have a low oxidation potential in the range of 0.1 to 1 V (inclusive) with respect to the Ag / AgCl electrode. The relatively low oxidation potential can be beneficial to the cycling durability of the ECP. Therefore, the electrochromic polymers of this disclosure can be successfully incorporated into devices with good cycling stability / reliability and high optical contrast.

[0039] MCL comprises at least one aromatic structure or condensed aromatic structure, or a combination thereof. In some embodiments, MCL comprises at least one benzene or naphthalene or condensed benzene structure or heterocycle or condensed ring structure or benzene condensed ring structure or a first benzene condensed with a ring structure condensed with a second benzene, or a combination thereof. In some embodiments, MCL comprises at least one benzene or naphthalene or condensed benzene structure or a five-membered heterocycle or condensed five-membered ring structure or a first benzene condensed with a five-membered ring structure condensed with a second benzene, or a combination thereof. Side chains or aromatic side chains can also be introduced onto MCL to modify the performance of MCL, for example, solubility or processability or stability.

[0040] In some embodiments, one or more MCLs and one or more Ars are arranged in an alternating or random manner according to the following general formula.

[0041] [ka]

[0042] In this structure, n is an integer greater than 0, and m1, m2, ..., m n Each of them is a non-negative integer, where m1, m2, ..., m n At least one of the values ​​is greater than 0. One or more Ars are aromatic moieties, and an aromatic moiety may contain one or more aromatic structures. Each of the one or more MCLs (or Ars) may be the same as or different from one another.

[0043] Metaconjugation is introduced into the polymer backbone by the use of one or more MCLs. Each of the one or more MCLs is partially conjugated in the polymer backbone by linking with one or more Ar atoms through their meta positions. For example, the meta positions are two positions in the aromatic or condensed aromatic structure of the MCL. When linked at meta positions, the π electrons from the aromatic or condensed aromatic structure cannot be completely delocalized to another adjacent linked unit through the p orbitals.

[0044] In some embodiments, the aromatic structure of MCL includes a benzene structure, and the aromatic structure of MCL is substituted at the meta position (positions 1 and 3, or 2 and 4, or 3 and 5 on the aromatic structure). In some embodiments, the aromatic structure of MCL includes a five-membered heterocyclic structure, and the aromatic structure of MCL is substituted at the meta position (positions 2 and 4, or 3 and 5 on the aromatic structure). In some embodiments, the condensed aromatic structure of MCL includes naphthalene, and the condensed aromatic structure is substituted at the meta position, where the meta position is at positions 1 and 3, or 2 and 7, or 1 and 6 on the naphthalene. In some embodiments, if there are several substituents on the naphthalene structure, the position numbers may be changed by different nomenclature rules. When other condensed structures (such as benzene condensed with a five-membered heterocyclic structure, or benzene condensed with a five-membered heterocyclic structure condensed with benzene, or naphthalene condensed with a five-membered heterocyclic structure, or a condensed structure chemically bonded with another benzene, a five-membered heterocyclic structure, or naphthalene), or dibenzene, or dinaphthalene, or other structures having a benzene, naphthalene, or five-membered heterocyclic structure are chemically bonded, a complex nomenclature rule must be adopted, and the rules can become even more complex with various substituents. In some embodiments, the condensed aromatic structure of MCL includes benzene condensed with a five-membered heterocyclic structure, and the condensed aromatic structure is substituted at the meta position, where the meta position is at positions 3 and 5, or positions 2 and 5, on the benzene condensed heterocyclic structure.

[0045] One or more exemplary MCL structures and their corresponding meta positions may include at least one of the following:

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] (In the formula, X is S, Se, N, C, or O; R1~R 12 Each of them is hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Selected independently from one of the polyethylene glycol ethers (the wavy line indicates the meta position).

[0054] One or more Ars are [ka] It may include, but is not limited to, one of the following units having the formula benzene-based, or naphthalene-based, or fluorene-based, or thiophene-based, furan-based, selenofen-based, or pyrrole-based, or any combination thereof. In the above structure, R 13 ~R 15 and R 21 ~R 36 is a substituent; at least one substituent in each formula is C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of the polyethylene glycol ethers; each of the remaining substituents in each formula is hydrogen, C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 It is independently selected from one of the polyethylene glycol ethers. Each wavy line represents a position where it connects to an adjacent MCL.

[0055] Examples of units based on thiophene are not limited to, [ka] The formula may include, or a combination thereof. In the above structure, X is S, Se, N, C, or O; R 15 ~R 18 Each of them is hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Y is independently selected from one of the polyethylene glycol ethers. Y is one or more of Ar, an aromatic structure, or a condensed aromatic structure, or a combination thereof.

[0056] In some embodiments, the thiophene unit X is O.

[0057] Introducing metaconjugation to the electrochromic polymer backbone disrupts electron conjugation along the polymer backbone, leading to a high band gap (>2.0 eV). Consequently, the electrochromic polymers of this disclosure appear highly transmissive (or even transparent) in a neutral state. Oxidation of the ECP results in a lower band gap (<1.5 eV), and the polymer's absorption is red-shifted from the UV region to the visible and near-infrared regions. Consequently, the polymer becomes highly colored.

[0058] One or more Ars may include one or more aromatic structures or condensed aromatic structures. By controlling the type and amount of Ar, the redox potential of the electrochromic polymer of the present disclosure can be easily adjusted while maintaining high transparency within the visible light range in the neutral state. For example, introducing units richer in electrons (e.g., dioxythiophene) onto the main chain makes the polymer more easily oxidized, resulting in a decrease in its onset potential and improvement in its electrochemical stability and electrochromic cycling stability. By changing the substituents on the MCL (e.g., introducing an alkoxy side chain), the redox potential of the electrochromic polymer of the present disclosure can also be adjusted.

[0059] The disclosed electrochromic polymer can be dissolved in a solvent, such as toluene or p-xylene, and used in a solution-processable film casting process. By controlling the concentration of the polymer solution, a polymer thin film with a controllable thickness can be obtained. Furthermore, the excellent solubility leads to the compatibility of the electrochromic polymer of the present disclosure with various casting methods, such as spin coating, spray coating, and drop casting. A more extensive application becomes possible with a process friendly to manufacturing.

[0060] Examples are shown below.

Example

[0061] Embodiment

[0062] <Example 1: ECP-1> In some embodiments, ECP-1 of the present disclosure has the following formula.

Chemical formula

[0063] ECP-1 is synthesized by preparing a carbazole-containing reaction unit and then polymerizing it with a dimer unit. The detailed method includes the following steps:

[0064] Step 1: Preparation of the carbazole-containing reaction unit (compound 2). [ka]

[0065] 3,6-Dibromocarbazole is dissolved in DMF. Then, 1.2 equivalents of NaH are added and the mixture is stirred for 2 hours. Next, 1.2 equivalents of compound 1 are added to the reactants and the mixture is stirred overnight. Then, water is added to the reactants and the solid is precipitated. The suspension is filtered to obtain the desired product, compound 2, as a white solid.

[0066] Step 2: Polymerization: Polymerization of carbazole-containing reaction units with dimer units. [ka]

[0067] Compound 2 (1 equivalent), Compound 3 (1 equivalent), K2CO3 (2.6 equivalents), PivOH (0.3 equivalents), and Pd(OAc)2 (0.02 equivalents) were placed in a Schlenk tube. The tube was then vacuumed (for 3-5 minutes) and refilled with nitrogen. This procedure was repeated three times. Subsequently, dimethylacetamide (DMAc), a solvent degassed with nitrogen, was added, and the mixture was heated to 120°C and maintained for 14 hours. The mixture was then poured into methanol to precipitate the crude polymer solid. The mixture was filtered to obtain the solid, which was redissolved in chloroform and washed three times with water. The chloroform solution was added to a large amount of methanol to precipitate the polymer. The suspension was filtered to obtain the desired product, polymer ECP-1.

[0068] The resulting ECP-1 has an oxidation potential of approximately 0.75 V (vs. Ag / AgCl) and an energy band gap higher than 3.0 eV. ECP-1 is assembled into a solid-state ECD using ECP-1 as the electrochromic layer, 0.2 M LiTFSI in PEGDA as the electrolyte, and VOx as the ion storage layer. The solid-state ECD can be stably switched between -0.5 V and 1.5 V (Figure 2). The absorbance spectra of ECP-1 in the neutral and oxidized states are shown in Figure 4, along with λc at 405 nm and λmax at 320 nm. The solid-state ECD exhibits high transparency with a high transmittance of 93% in the neutral state (Figure 3), and when ECP-1 is oxidized, it switches to a vivid blue color with one absorption peak at approximately 614 nm and another broader absorption band in the near-infrared region of approximately 900-1100 nm (Figure 4). The optical contrast of solid-state ECDs is approximately 75% (Figure 3).

[0069] <Example 2: ECP-2> In some embodiments, the ECP-2 of this disclosure is given by the following formula: [ka] It holds.

[0070] ECP-2 is synthesized by first preparing substituted benzene reaction units and then polymerizing them with acyclic dioxythiophene (AcDOT) units. The detailed method includes the following steps:

[0071] Step 2-1: A step in which a benzene-containing reaction unit (compound 4) is prepared by two steps. [ka]

[0072] Compound 5 and p-toluenesulfonic acid are dissolved in acetonitrile. Then, N-bromosuccinimide is added and the mixture is stirred overnight. The suspension is filtered to obtain the desired product. The product, compound 6, is a white solid.

[0073] [Chem.]

[0074] Dissolve Compound 6 in DMF under N2. Add K2CO3 to the solution, stir the reaction mixture for 15 minutes, and then add 2-ethylhexyl bromide (2-ethylhexyl bromide). Stir the reaction mixture at 100 °C overnight. Stop the reaction and cool to room temperature. Remove the solvent in vacuo, dissolve the residue in diethyl ether. Wash the organic phase with water and extract the aqueous phase with ethyl acetate. Dry the combined organic phases and remove the volatile substances under vacuum. Pass the stock solution through a small silica column, dry the solvent in vacuo, and obtain Compound 4 as a yellow oil.

[0075] Step 2-2: Polymerization: The polymerization method is similar to that in Step 1-2, using the reaction units of the substituted benzene reaction unit (Compound 4) and AcDOT (Compound 8) having the following structure. [Chem.]

[0076] The obtained ECP-2 has an oxidation potential of approximately 0.95 V (vs. Ag / AgCl) and an energy band gap higher than 3.1 eV. ECP-2 is assembled into a solid-state ECD using ECP-2 used as an electrochromic layer, 1 M LiPF6 in PEGMEA as an electrolyte, and VO x as an ion storage layer. This solid-state ECD can be stably switched between -0.6 V and 1.7 V (Figure 5). The absorbance spectra of the neutral and oxidized states of ECP-2 were measured at wavelengths of 410 nm c and 350 nm maxThis is shown in Figure 7. The solid-state ECD exhibits high transparency, with a high transmittance of 94% at 550 nm in the neutral state (Figure 6). When ECP-2 is oxidized, it exhibits one absorption peak at approximately 546 nm and another broader absorption band at wavelengths of approximately 800–1100 nm (Figure 7), switching to a vivid red color. The optical contrast of the solid-state ECD is 87% (Figure 6).

[0077] <Example 3: ECP-3> In some embodiments, the ECP-3 of this disclosure has the following formula. [ka]

[0078] ECP-3 is synthesized by preparing benzene-containing reaction units and polymerizing them with ProDot units. The detailed method includes the following steps:

[0079] Step 3-1: Same as Step 2-1.

[0080] Step 3-2: Polymerization: The polymerization method is similar to that of Step 1-2, using different reaction units: a benzene-containing reaction unit (compound 4) and 3,4-ethylenedioxythiophene (EDOT, compound 9) having the structure described below. [ka]

[0081] <Example 4: ECP-4> In some embodiments, the ECP-4 of this disclosure has the following formula: [ka]

[0082] ECP-4 is synthesized by preparing naphthalene-containing reaction units and then polymerizing them with AcDOT units. The detailed method includes the following steps:

[0083] Step 4-1: A naphthalene-containing reaction unit (compound 10) is prepared through two steps. [ka]

[0084] A solution of bromine in dichloromethane was added dropwise to a solution of compound 11 in dichloromethane over 15 minutes at -78°C. The reaction mixture was stirred at -78°C for 2 hours, then gradually warmed to room temperature and left at room temperature for another 2 hours. Excess bromine was deactivated with saturated sodium sulfite aqueous solution, and the mixture was stirred at room temperature for 2 hours. After extraction with dichloromethane, the combined organic phase was washed with brine, dried on sodium sulfate, and concentrated under vacuum.

[0085] [ka]

[0086] Compound 12 is dissolved in DMF under N2 conditions, K2CO3 is added to the solution, the reaction mixture is stirred for 15 minutes, and then 2-ethylhexyl bromide is added. The reaction mixture is stirred overnight at 100°C. The reaction is stopped and allowed to cool to room temperature. The solvent is removed under vacuum, and the residue is dissolved in diethyl ether. The organic phase is washed with water, and the aqueous phase is extracted with ethyl acetate. The combined organic phase is dried under vacuum.

[0087] Step 4-2: Polymerization: The polymerization method is similar to that of Step 1-2, but uses different reaction units: a naphthalene-containing reaction unit (compound 10) and AcDOT (compound 8).

[0088] <Example 5: ECP-5> In some embodiments, the ECP-5 of this disclosure has the following formula. [ka]

[0089] ECP-5 is synthesized by a polymerization method similar to that of steps 1-2, using different reaction units: 1,5-dibromo-2,4-bis(hexyloxy)benzene and 3,4-dimethylthiophene.

[0090] In some embodiments, the ECP of this disclosure has the following formula.

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] (In the formula, n and m are integers greater than 0, and a and b are integers greater than or equal to 0, provided that at least one of a and b is greater than 0.) It holds.

[0096] In another embodiment, the polymers of the present disclosure may have fluorescent emission and may be applied to fluorescent products.

[0097] In conventional conjugated electrochromic polymers, the formation of polarons and bipolarons through electrochemical doping reduces the energy of optical transitions, resulting in a redshift of absorption from the visible to the near-infrared region, which manifests as a change from color to transmission. Consequently, in the doped state, absorption remains throughout the visible region. As the film thickness increases, this residual absorption intensifies, and residual color appears. Thus, conjugated electrochromic polymers have relatively low optical contrast and contrast ratio, which is a major factor limiting their further adoption in polymer-based ECD applications.

[0098] In contrast to conventional conjugated ECPs that induce a transition from colored to transparent states, the novel ECPs disclosed herein induce a transition from transparent to colored states. Because the disclosed polymers exhibit a higher energy band gap, they absorb light in the ultraviolet region without absorbing in the visible region in the neutral state, resulting in a transparent state, and in some embodiments, nearly 100% transparency. For example, polymers containing the chromophore triarylamine achieve electrochromic switching from transparent to colored. Conventional small molecules based on ethylenedioxythiophene derivatives can switch from transparent to colored states. However, such designs present unique challenges. Firstly, these polymers typically have poor switching stability. This is because the charges formed in the doped state cannot be delocalized along the polymer chain, limiting stability and durability. Secondly, because electrochromic elements based on organic small molecules are typically in a solution phase, the color change depends on the diffusion of molecules onto the electrode, resulting in slow switching speeds, intermediate colors, and hindering applications in flexible devices.

[0099] The electrochromic polymers disclosed herein exhibit nearly 100% transmittance (e.g., 85%–99.9%) in a neutral state, while showing high absorption in an oxidized state, resulting in the highest recorded optical contrast and contrast ratio. The polymer backbone, as described above, includes or consists solely of a meta-conjugated linker (MCL) and an aromatic moiety (Ar). The MCL conjugates the aromatic moiety at the meta position, interrupting charge delocalization. Thus, the band gap of the disclosed polymer is increased by meta-conjugation, concentrating the absorption of the neutral polymer in the ultraviolet region and achieving nearly 100% transparency. On the other hand, the MCL and aromatic moiety conjugate, resulting in a low oxidation potential and high switching stability for switching from transparent to colored. The color of the polymer can be easily controlled by adjusting the conjugation length of the MCL and aromatic moiety. In some embodiments, the disclosed polymers can be made from MCL such as carbazole, biphenyl, or binaphthalene, and thiophene as the aromatic moiety. The polymers disclosed based on the concept of this invention exhibit broad color tuning capabilities and good electrochromic properties, including optical contrast of over 95% and switching stability of over 10,000 cycles.

[0100] The optical contrast of the disclosed electrochromic film increases with increasing film thickness. While increasing the thickness of the EC film may increase the response time, this can be reduced through various device optimizations, such as coating techniques and materials for each layer. Table 1 summarizes theoretical predictions regarding the relationship between film thickness and transmittance in neutral and oxidized states, based on a function derived from a series of experimental data for thicknesses less than 1000 nm. Optical contrast is obtained by subtracting the transmittance in the neutral state from the transmittance in the oxidized state. As shown in Table 1, it is predicted that the transmittance in the bleached (white) / neutral state decreases as the thickness increases, which is consistent with conventional understanding. However, experimental data using the electrochromic layers of this disclosure with thicknesses exceeding 1000 nm reveal surprising results. As shown in Table 2, even when the film thickness increases to approximately 3500 nm, the transmittance in the neutral state hardly changes compared to the transmittance of thinner films. Considering the detection limits of the instrument, films thicker than 3500 nm remain unverified. However, based on the inventors' knowledge, it can be very reasonably inferred that the transmittance of the disclosed electrochromic polymer in a neutral state remains largely unchanged even at film thicknesses up to 5800 nm. It has also been confirmed that even with increasing film thickness, only slight changes are observed in the high transmittance of the disclosed new type of electrochromic polymer. Depending on the chemical structure, measurement variations, and operating settings, in some embodiments, an electrochromic layer thickness of 10 nm to 5800 nm may result in a transmittance of 70% to 99.9% at wavelengths of 550 nm or 416 nm (depending on the type of disclosed electrochromic polymer) in a neutral state. For example, if the thickness of the electrochromic layer 106 is between 10 nm and 5800 nm, the transmittance will be 70%, 75%, 80%, 85%, 87%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 99.9%, or any two of the above values.

[0101] [Table 1]

[0102] [Table 2]

[0103] When the film thickness is greater than 1500 nm, the disclosed electrochromic (EC) element can have a large optical contrast, for example, a transmittance of approximately 96% in the neutral state and approximately 0.06% in the oxidized state of the EC layer, and the element can have a slow response time, for example, approximately 1 minute. However, it is possible to shorten the response time by various element optimizations, such as coating techniques and materials for each layer. As the film thickness increases, the transmittance of the EC layer in the neutral state may decrease slightly. However, the transmittance of the EC layer in the oxidized state may decrease significantly, so the optical contrast of the EC layer (the difference in transmittance between the neutral and oxidized states) increases significantly with increasing film thickness. Therefore, it becomes possible to design various EC films that can be used in the same electrochromic element, for example, for dynamic contrast applications. For high-contrast applications with high response time tolerance, such as smart windows, advertising displays, and architectural interior design, the film thickness can be selected from 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, or 1500nm, 2000nm, 2500nm, 3000nm, 3500nm, 4000nm, 4500nm, 5000nm, or 5500nm, or any two of the above values. For applications requiring high contrast and low response time, such as vehicle mirrors, sunshades, screens, and displays, the film thickness can be selected from 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, 1100nm, 1200nm, 1300nm, 1400nm, or 1500nm, or any two of the above values.

[0104] [Examples] In the disclosed polymers, each metaconjugated polymer contains an aromatic comonomer linked at the meta position by MCL. A series of polymers are designed by varying the number of thiophenes (T1, T2, and T3) to alter the length of the aromatic moiety, with MCLs including carbazole (CBZ), biphenyl (BP), and binaphthalene (BNP). The structures of these designs are shown below.

[0105] [ka]

[0106] To guide the experiment and explore design paradigms from a molecular orbital perspective, density functional theory (DFT) calculations were performed on these metaconjugated polymers to create theoretical spectra for neutral and radical cation states. The absorption spectra of CBZ-T1, BP-T1, and BNP-T1 in the neutral state show nearly 100% transparency in the visible region, with significant absorption occurring only in the ultraviolet region (Figure 8(A)). CBZ-T1 and BNP-T1 show a slight redshift in absorption onset compared to BP-T1, but all three polymers maintain absorption wavelengths below 400 nm. In the radical cation (oxidized) state, absorption in the ultraviolet region decreases, and absorption in the visible region increases (Figure 8(B)). This electrochromism from transparency to color can be further explained by the geometric change of the polymer from neutral to radical cation state. In the neutral state, the polymers adopt a non-planar structure with a twist angle of approximately 50-60 degrees between the MCL and the adjacent thiophene. This non-planar structure and large torsional impediment hinder charge delocalization and increase the band gap of the neutral polymer, causing the polymer to absorb only in the ultraviolet region. On the other hand, in the radical cation state, the polymer becomes flatter as the torsional angle decreases to 25-40 degrees, so charges can delocalize along the polymer chain, and absorption redshifts into the visible region for coloration. In contrast to BP-T1, the radical cation absorption of CBZ-T1 and BNP-T1 is more redshifted due to the expansion of conjugation from the BNP unit.

[0107] The length of the aromatic moiety affects the optical properties of the polymer. In the neutral state, CBZ-T1, CBZ-T2, and CBZ-T3 exhibit nearly identical absorption spectra, suggesting that the number of thiophene units does not affect the polymer's band gap in the neutral state. Based on calculations, the twist angle between MCL and thiophene remains nearly constant throughout the polymer even as the number of thiophene units increases, resulting in corresponding absorption in the ultraviolet region and transparency. However, in the radical cation state, increasing the number of thiophene units causes a redshift in the spectrum. As a result, the radical cation polymers exhibit distinct colors, specifically orange, purple, and blue, corresponding to CBZ-T1, CBZ-T2, and CBZ-T3, respectively. This color change is thought to be due to a large change in the twist angle between thiophene units. A change in the twist angle (approximately 5 degrees) was observed when thiophene units transitioned from one polymer (CBZ-T1) to two polymers (CBZ-T2). A similar trend was observed during the transition from 2T to 3T, with torsion angles of approximately 15 degrees in each case. MCL may prevent charge delocalization of neutral polymers, resulting in nearly 100% transparency. The color of polymers in the radical cation state can be tuned by adjusting / changing the conjugation length of the polymer.

[0108] <Examples of electrochromic polymer synthesis> MCL monomers of carbazole, biphenyl, and binaphthalene are synthesized with different extended conjugations. Different side chains are added to the MCL to adjust the solubility and polarity of the polymers. Next, oligomers 3,4-dimethylthiophene T1, T2, and T3 are made. After obtaining the monomers, direct arylation polymerization (DArP) is performed to create nine meta-conjugated transparent electrochromic polymers. Each meta-conjugated polymer solution is spin-coated onto ITO glass as a working electrode and placed in a cuvette for electrochemical and optical measurements. The position of the absorption peak in the oxidized state shows a red-shift tendency due to the incorporation of longer aromatic moieties. The disclosed technique allows for a reasonable shift of the absorption peak, thus providing access to a wide variety of colors across the visible region. In some embodiments, oxidized polymers with different aromatic moiety lengths exhibit distinct colors, specifically orange, violet, and blue, corresponding to T1, T2, and T3 of the BP and CBZ polymers, respectively. CIELAB color coordinates are obtained for all polymers in neutral and oxidized states. The polymers in the neutral state are L * a * b *The values ​​are close to (100,0,0) and are completely transparent. In the oxidized state, these polymers cover a wide range of color space and are mixable. By varying the lengths of one or more MCL and one or more Ar conjugates, the disclosed electrochromic polymers can be controlled to design a wide range of colors. Furthermore, by blending different disclosed electrochromic polymers of different colors in different ratios, batches of different colors can be produced, thereby greatly enriching the color library. Moreover, unlike conventional electrochromic polymer blends, because the oxidation potentials of the disclosed electrochromic polymers are close, the disclosed electrochromic polymer blends do not have the intermediate color problem commonly observed in conventional electrochromic polymer blends. In some embodiments, due to their high transmittance, the disclosed electrochromic polymers or blends have high optical contrast and good stability, with a large color library without intermediate colors. The disclosed electrochromic polymer / device can be used in a variety of applications, including smart windows and glass, biosensors, electronic paper, displays, augmented reality (AR), virtual reality (VR), mixed reality (MR), patterned electrochromic displays, curtain walls, and sunroofs.

[0109] The electrochemical properties of the polymers are evaluated by cyclic voltammetry and differential pulsed voltammetry (DPV). The polymers exhibit quasi-reversible oxidation. When the polymers are examined by DPV, CBZ-T1, CBZ-T2, and CBZ-T3 show one peak indicating the formation of a radical cation. However, polymers containing BP and BNP units show two peaks, with a second peak corresponding to the formation of a dication. This oxidation makes the electrochemistry irreversible, and a new absorption peak is formed in the visible region. It is noteworthy that all polymers exhibit relatively low oxidation onset potentials (CBZ polymers approximately 0.6–0.8V (vs. Ag / AgCl), BP polymers approximately 0.8–1.0V (vs. Ag / AgCl), and BNP polymers approximately 0.8–1.0V (vs. Ag / AgCl)), which is due to conjugation from the aromatic moiety. Low oxidation onset potentials are beneficial for the electrochemical stability of the polymers because they avoid undesirable side reactions such as the oxidation of water. While these metaconjugated polymers have similar properties, CBZ polymers generally have lower oxidation initiation potentials and superior reversibility at high potentials.

[0110] The lower energy absorption peaks result from electron spin-down, specifically from the singly occupied molecular orbital (Sβ) to the lowest unoccupied molecular orbital (Lβ). Thus, the disclosed metaconjugated polymers can synchronously modulate both visible light and near-field IR.

[0111] The disclosed technology enables the color tuning and low oxidation potential of meta-conjugated electrochromic polymers. Using this technology, black electrochromism can also be achieved by blending chromophores of vivid colors whose collective absorption completely covers the visible spectrum. The inventors have found that desired colors can be obtained by blending the disclosed polymers. In some embodiments, CBZ-T1 (orange) and CBZ-T3 (blue) meta-conjugated polymers are blended to obtain electrochromism ranging from transparent to black. When blending, the absorption coefficients of the polymers in their oxidized states are used to determine the appropriate ratio of polymers to blend to obtain black. Beer-Lamber plots of the polymer films show that the absorption coefficients of CBZ-T1 and CBZ-T3 in their oxidized states are approximately the same, and therefore the mass ratio of the CBZ-blend is determined to be 1:1. Other mass ratios of blends, or blends of different disclosed polymers, can be used to create other desired colors.

[0112] The absorption spectroscopy and electrochemistry of a CBZ blend with a film thickness of 300 nm is shown in Figure 9(A). This neutral film shows absorption initiation at 400 nm and exhibits nearly 100% transparency in the visible region. When the CBZ blend is oxidized to a radical cation state, two broad absorptions with λmax at 550 nm and 950 nm occur in the visible and near-IR regions, indicating that light and heat are modulated synchronously. Numerous CBZ blend films with different film thicknesses were prepared, and the absorption coefficients were derived from Beer-Lambert plots, as shown in Figure 9(B). The absorption coefficient of the neutral (bleached) CBZ blend is 5 × 10⁻¹⁰. 2 cm -1 It is estimated that the oxidation (coloring) state value is 3.7 × 10 4 cm -1It is two orders of magnitude lower. As shown in Figure 9(C), the transmittances in the neutral and oxidized states are plotted as a function of film thickness using the respective absorption coefficients. When the film thickness is thin, the transmittance can be brought close to 100% in both the neutral and oxidized states. Since the absorption coefficient in the neutral state is close to zero, the transmittance remains almost 100%, and attenuation is minimized even as the film thickness increases. In some embodiments, the optical contrast between the neutral and oxidized states can reach almost 100%, for example, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or higher, or any of the above values. Figure 9(D) shows the transmittances of CBZ-blends in both the neutral and oxidized states of electrochromic layers of different thicknesses according to some embodiments. The optical contrast is equal to the difference in transmittance between the neutral and oxidized states. For different film thicknesses (270–700 nm) measured in a neutral state, the optical contrasts shown in Figure 9(D) are 78, 87.7, 92.1, 93.3, and 92, respectively. The contrast ratio is calculated by the ratio of transmittance in the neutral state to transmittance in the oxidized state. For different film thicknesses (270–700 nm) measured in a neutral state, the contrast ratios shown in Figure 9(D) are 4.9, 9.8, 19.4, 47.65, and 93, respectively. As shown in Figure 9(D), the optical contrast of the disclosed electrochromic film increases with increasing film thickness. As the thickness of the disclosed EC film increases, the response time increases. When the film thickness is greater than 1500 nm, the disclosed EC element can have a large optical contrast, for example, a transmittance of about 96% in the neutral state and about 0.06% in the oxidized state of the EC layer, and the element can have a slow response time, for example, about 1 minute. Further optimization of the element can shorten the response time. As the film thickness increases, the transmittance of the EC layer in the neutral state may decrease slightly. However, the transmittance of the EC layer in the oxidized state may decrease significantly, so the optical contrast of the EC layer (the difference in transmittance between the neutral and oxidized states) increases significantly with increasing film thickness. In applications where high optical contrast is strongly required, but a slow response time is acceptable, the disclosed EC layer thickness can reach up to 5800 nm.In applications where response speed is critical, in some embodiments, the thickness of the disclosed EC layer is limited to 1500 nm or less. In some embodiments, the thickness of the disclosed EC layer is limited to 1200 nm, 1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, or 100 nm to obtain a response time of less than 10 seconds.

[0113] The disclosed meta-conjugated electrochromic polymer layer exhibits ultra-high optical contrast and fast switching speed. It also demonstrates high stability, including photostability and electrochromic switching stability. Photostability was investigated by exposing the encapsulated polymer film to a solar simulator adapted to a standard air mass of 1.5 light source. Absorption spectra were measured, and maximum absorption was plotted as a function of irradiation time. This result indicates that the disclosed polymer is stable even when used in combination with other materials such as ITO, electrolytes, and ion storage layers (e.g., nano-ITO particles). To clarify the cyclic stability of the polymer film, 10,000 CV switching cycles were applied in a three-electrode setup, applying a voltage from -0.2V to 1.0V at 80mV / s. Transmittances in neutral and colored states were recorded every 1000 cycles. The optical contrast of the polymer decreased by 10%, suggesting that the meta-conjugated polymer is suitable for long-term performance.

[0114] As shown in Figure 10, an electrochromic element 100 according to some exemplary embodiments may have a first insulating substrate 102, a first conductive layer 104 disposed on the first insulating substrate 102, an electrochromic layer 106 disposed on the first conductive layer 104, an electrolyte layer 108 disposed on the electrochromic layer 106, a second conductive layer 112 disposed on the electrolyte layer 108, a second insulating substrate 114 disposed on the second conductive layer 112, and a circuit 116 for operating the electrochromic element 100. In some embodiments, the electrochromic element 100 may further include an ion storage layer 110 disposed between the second conductive layer 112 and the electrolyte layer 108. The electrochromic layer 106 may include the electrochromic polymer disclosed above. For example, an electrochromic polymer comprises, or consists solely of, a polymer backbone containing one or more metaconjugated linkers (MCLs) and one or more aromatic moieties (Ar), each of which is partially conjugated to one of the Ars at the meta position of the MCL. In some embodiments, the thickness of the electrochromic layer 106 is 10 nm to 800 nm, resulting in a transmittance of 70% to 99.9% at a wavelength of 550 nm in the neutral state of the electrochromic layer. For example, when the thickness of the electrochromic layer 106 is 10 nm to 5800 nm, transmittances of 70%, 75%, 80%, 85%, 87%, 90%, 92%, 95%, 96%, 97%, 98%, 99%, 99.9%, or any two of the above values ​​can be obtained. The electrochromic element 100 has a transmittance of 50% or more at a wavelength of 550 nm in its bleached state. For example, by adjusting the material and thickness of the electrochromic layer 106, the electrochromic element 100 may have a transmittance of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92%, 95%, 96%, 97%, 98%, or 99% in its bleached state, or any two of the above values.

[0115] In some embodiments, the electrochromic layer has a transmittance of 40% to 0.1% at a wavelength of 550 nm when in an oxidized state. For example, the electrochromic layer in an oxidized state has a transmittance of 40%, 35%, 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% at a wavelength of 550 nm, or any two of the above values.

[0116] In some embodiments, the electrochromic layer 106 has an optical contrast of 60% or more. For example, the electrochromic layer 106 may have an optical contrast of 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or any two of the above values.

[0117] In some embodiments, when the electrochromic element 100 includes an ion storage layer 110, the ion storage layer 110 has a transmittance of 80% or more at a wavelength of 550 nm. In some embodiments, the ion storage layer 110 may include (1) one or more oxides of metal elements from groups 4 to 12, or (2) a mixture of oxides, or (3) one oxide doped with different metal oxides, or (4) a transition metal complex, or (5) one or more redox-active polymers including redox-active nitroxyl, galbinoxyl radical polymers, and conjugated polymers.

[0118] In some embodiments, the ion storage layer 110 contains ITO particles, and the ion storage layer has a transmittance of 90% or more at a wavelength of 550 nm. In some embodiments, the ITO particles may be nanoparticles having a size of 1 to 900 nm.

[0119] In some embodiments, at least one of the first conductive layer 104 and the second conductive layer 112 includes ITO, zinc aluminum oxide (AZO), fluorine-doped tin oxide (FTO), silver nanowires, graphene, carbon nanotubes, metal mesh-based transparent conductive electrodes, silver nanoparticle ink, or an organic conductive polymer.

[0120] In some embodiments, the electrochromic element 100 has an optical contrast of 60% or more. For example, the electrochromic element 100 may have an optical contrast of 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, or any two of the above values.

[0121] In some embodiments, the color of the electrochromic layer 106 in the oxidized state is changed by varying the conjugation lengths of one or more MCL and one or more Ar.

[0122] In some embodiments, the electrochromic layer 106 comprises a blend of different electrochromic polymers that do not contain intermediate colors. The polymer(s) structures of the electrochromic layer 106 have been described above and will not be repeated for brevity.

[0123] This disclosure further provides an electrochromic element that can switch between transparent and black states. Electrochromic materials that can reversibly switch between a black state and a transparent state are of great importance for a variety of commercial and military applications. For example, the inventors discovered that CBZ-T1 and CBZ-T3 have similar absorption coefficients, and by mixing CBZ-T1 (switching from transparent to orange) and CBZ-T3 (switching from transparent to blue) in a 1:1 mass ratio, a transparent-to-black electrochromic element is obtained. The configuration of the transparent-to-black electrochromic element is the same as that of the electrochromic element 100 described above. This element is assembled in a two-electrode configuration by using a mixture of CBZ-T1 and CBZ-T3 as the electrochromic layer and nano-ITO particles as the ion storage layer (1.5 μm). Spectroelectrochemical studies show that the potential of the element increases from -0.6V to 2.4V. As the potential increases, oxidation of the CBZ-T1 and CBZ-T3 mixture reduces the transmittance in the visible region, and the element switches from a transparent state to a black state. Increase the potential until no further change in transmittance is observed and the optical contrast reaches 88% (1-89%). The transmittance spectrum is air-referenced, meaning that transmittance loss includes glass, ITO, electrolyte layer, and ion storage layer. CIE L at different voltages * a*b * Investigate the color coordinates. As the potential increases, CIE L * a * b * Color coordinate brightness (L * ) decreased from 95 to 36, a * and b * The value remained close to 0, indicating a color switching from transparent to black without any intermediate colors. To reveal the cycle stability of the device, 10,000 CV switching cycles were applied and the transmittance spectra were measured. The transmittance at 550 nm in the transparent and colored states of the device shows a slight decrease in optical contrast from the original value of 85% to 78% (shown in Figure 9(E)), representing the best cycle stability for a black electrochromic device with such high optical contrast.

[0124] In summary, this disclosure provides a metaconjugated polymer that enables transparent-to-colored electrochromic switching, exhibiting a wide color gamut, ultra-high optical contrast, low oxidation potential, and excellent switching stability. The transparent-to-black electrochromic elements based on the polymer blend successfully achieve optical contrast exceeding 91% and a contrast ratio of 91%, demonstrating the best performance among black electrochromic elements. This approach to accessing transparent electrochromic polymers opens up promising prospects for future electrochromic innovations.

[0125] Another aspect of this disclosure discloses another novel design for obtaining an electrochromic polymer having an absorption onset of 420 nm or less in a neutral state and having at least one absorption peak between 390 and 460 nm, including both ends, in an oxidized state. This novel structural design can also be used to synthesize electrochromic polymers having absorption peaks at wavelengths higher than 460 nm in an oxidized state, such as 465 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, or any wavelength in between.

[0126] <The significance of designing electrochromic polymers that have a single absorption peak between 390 and 460 nm, including both ends, in the oxidized state.> To achieve high optical contrast, high transmittance, and synergistic solar heat acquisition, the inventors have created a type of metaconjugated polymer disclosed above, in which absorption onset is 420 nm or less. A key feature of this design is the polymer backbone, in which metaconjugated linkers (MCLs) and aromatic moieties (Ar) are alternately linked. Each MCL is partially conjugated in the polymer backbone by alternate linking to each Ar through the meta position. The metaconjugated linkers induce partial conjugation by introducing non-conjugated segments into the conjugated polymer, thereby inhibiting charge delocalization and increasing the polymer's band gap. Absorption of the neutral polymer is concentrated in the ultraviolet region, and in the neutral state, high transmittance and colorlessness can be achieved. When oxidation occurs, light absorption shifts to the visible light region, resulting in coloration. Due to its colorlessness, primarily in the neutral state, the electrochromic polymer of this disclosure can achieve high optical contrast. The alternating MCL and Ar design strategy described above has resulted in the creation of various orange, purple, and blue electrochromic polymers in the oxidized (colored) state, exhibiting absorption peaks in the 460–700 nm range. However, intensive efforts to synthesize polymers with absorption peaks in the 390–460 nm range, including both ends, in the oxidized state using previously reported alternating design have failed. Nevertheless, obtaining electrochromic polymers with absorption peaks in the 390–460 nm range is extremely important. On the other hand, as one of the primary colors based on traditional color theory and the RGB additive model, yellow or green is essential for creating a wide variety of other colors. When a polymer absorbs light in the 390–460 nm range, it exhibits yellow. If, in addition to 390–460 nm absorption, the polymer has other absorptions above 600 nm and an absorption trough around 500–560 nm, the polymer exhibits green. Conversely, even if the polymer does not exhibit yellow or green, the absorption contribution from 390 nm to 460 nm can generate a wide range of other colors. There is a strong need for novel design strategies to obtain electrochromic polymers that exhibit an absorption peak between 390 nm and 460 nm in the oxidized state and have absorption initiation below 420 nm in the neutral state.

[0127] In the following disclosure, a novel design strategy and a new type of electrochromic polymer are presented. The novel electrochromic polymer according to the novel design strategy disclosed in this application is [Chemical Formula] includes the formula of. In this formula, MCL represents a meta-conjugated linker, and Ac represents an aromatic moiety. Here, y is an integer greater than or equal to 0, n and x are integers greater than 1; a, b, c, d,..., m, a', b', c', d',..., m' are the ratios of the monomers in the electrochromic polymer; the sum of a, b, c, d,..., m, a', b', c', d',..., m' is equal to 1, 0 < each of a and b < 1, 0 ≤ each of c, d,..., m, a', b', c', d',... and m' < 1; the sum of a', b', c', d',..., m' is less than or equal to the sum of a, b, c, d,....

[0128] MCL includes at least one of an aromatic structure or a condensed aromatic structure, or a combination thereof. In some embodiments, MCL is benzene, or naphthalene, or a condensed benzene structure, or a heterocyclic ring, or a condensed ring structure, or a benzene-condensed ring structure, or at least one of a first benzene condensed with a ring structure condensed with a second benzene, or a combination of these structures. In some embodiments, each of MCL (MCL1, MCL2, MCL3, MCL4,..., and MCL x ) and the corresponding meta-position includes one of the following formulas.

[0129] [Chemical Formula]

[0130] [Chemical Formula]

[0131] [Chemical Formula]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] Ac1, Ac2, Ac3, Ac4, ..., Ac y Each of them is given by the following formula: [ka] A unit based on benzene, or a unit based on naphthalene, or a unit based on fluorene, or a unit based on pyrrole, or a unit based on thiophene, where X is S, Se, N, C, or O; each dash represents a position that links to an adjacent aromatic structure from MCL or Ac.

[0136] If each of c, d, ..., m, a', b', c', d', ..., m' is equal to 0, then in each MCL, R1~R 12 At least one of them is C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C30 Alkylsulfonyl, C3 - C 30 Alkylsulfonylalkyl, C6 - C 18 Aryl, C3 - C 15 Cycloalkyl, C3 - C 30 Cycloalkylaminyl, C5 - C 30 Cycloalkylalkylaminyl, C5 - C 30 Cycloalkylalkyl, C5 - C 30 Cycloalkylalkyloxy, C1 - C 12 Heterocyclyl, C1 - C 12 Heterocyclyloxy, C1 - C 30 Heterocyclylalkyloxy, C1 - C 30 Heterocyclylaminyl, C5 - C 30 Heterocyclylalkylaminyl, C2 - C 12 Heterocyclylcarbonyl, C3 - C 30 Heterocyclylalkyl, C1 - C 13 Heteroaryl, C3 - C 30 Heteroarylalkyl, C2 - C 30 Polyethylene glycol, or one of C3 - C 30 Polyethylene glycol ether.

[0137] When 0 < at least one of c, d, …, m, a’, b’, c’, d’, … and m’ < 1, in at least one Ac, at least one of R 21 ~R 36 and in at least one MCL, at least one of R1 - R 12 is C1 - C 30 Alkyl, C2 - C 30 Alkenyl, C2 - C 30 Alkynyl, C2 - C 30 Alkylcarbonyl, C1 - C 30 Alkoxy, C3 - C 30 Alkoxyalkyl, C2 - C 30 Alkoxycarbonyl, C4 - C 30 Alkoxycarbonylalkyl, C1 - C 30 Alkylthio, C1 - C 30 Aminylcarbonyl, C4 - C30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of the polyethylene glycol ethers, R 21 ~R 36 Each of the remaining ones, and R1~R 12 Each of the remaining ones is hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of the polyethylene glycol ethers. In some embodiments, in two or more or all of the Acs, R 21 ~R 36 In at least one and two or more or all MCLs, R1~R 12 At least one of them is C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 It is independently selected from one of the polyethylene glycol ethers.

[0138] The disclosed novel type of electrochromic polymer has absorption onset below 420 nm in a neutral state and absorption in visible and / or near-infrared wavelengths in an oxidized state. In some embodiments, the disclosed electrochromic polymer has absorption onset below 415 nm, 410 nm, 405 nm, or 400 nm in a neutral state. In some embodiments, the disclosed novel type of electrochromic polymer is colorless in a neutral state. In some embodiments, the disclosed novel type of electrochromic polymer has at least one absorption peak between 390 and 460 nm, including both ends, in an oxidized state. In some embodiments, the disclosed novel type of electrochromic polymer has at least one absorption peak between any two of the following values ​​(including both ends) in an oxidized state: 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm. In some embodiments, the disclosed novel type of electrochromic polymer is yellow or green in an oxidized state.

[0139] The novel types of electrochromic polymers disclosed can be synthesized by regular or random polymerization. In some embodiments, MCL1 is [ka] The formula is as follows: Here, R 20 C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3-C 30 Alkylsulfonylalkyl, C6-C 18 Aryl, C3-C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5-C 30 Cycloalkylalkylaminyl, C5-C 30 Cycloalkylalkyl, C5-C 30 Cycloalkylalkyloxy, C1-C 12 Heterocyclyl, C1-C 12 Heterocyclyloxy, C1-C 30 Heterocyclylalkyloxy, C1-C 30 Heterocyclylaminyl, C5-C 30 Heterocyclylalkylaminyl, C2-C 12 Heterocyclylcarbonyl, C3-C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3-C 30 Heteroarylalkyl, C2-C 30 Polyethylene glycol, or selected from one of C3-C 30 Polyethylene glycol ether; each of the wavy lines represents a position connecting to an adjacent aromatic structure from MCL or Ac. In some embodiments, each of 0 < a, b, c, a', b', and c' < 1, and each of d,..., m, d',..., m' in the disclosed new type of electrochromic polymer is equal to 0. In some embodiments, each of 0 < a, b, c, a' < 1, and each of d,..., m, b', c', d',..., m' in the disclosed new type of electrochromic polymer is equal to 0. The sum of a', b', c', d',..., m' is less than or equal to the sum of a, b, c, d,..., m. When the sum of a', b', c', d',..., m' is equal to the sum of a, b, c, d,..., m, in some embodiments, one MCL is directly connected to another MCL, and in some embodiments, one MCL is not directly connected to another MCL.

[0140] In some embodiments, Ac1, Ac2, Ac3, Ac4, ..., Ac y Each of these contains a thiophene unit, and the thiophene unit is expressed by the following formula: [ka] It includes one of the following. In these formulas, X is S, Se, N, C, or O; each tilde represents one of the meta positions. R 15 ~R 18 At least one of them is C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30 Independently selected from one of the polyethylene glycol ethers; R1~R 12 Each of the remaining ones is hydrogen, C1~C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkinyl, C2~C 30 Alkylcarbonyl, C1~C 30 Alkoxy, C3-C 30 Alkoxyalkyl, C2-C 30 Alkoxycarbonyl, C4~C 30 Alkoxycarbonylalkyl, C1~C 30 Alkylthio, C1~C 30 Aminylcarbonyl, C4~C 30 Aminylalkyl, C1~C 30 Alkylaminyl, C1-C 30 Alkylsulfonyl, C3~C 30 Alkylsulfonylalkyl, C6~C 18 Aryl, C3~C 15 Cycloalkyl, C3-C 30 Cycloalkylaminyl, C5~C 30 Cycloalkylalkylaminyl, C5~C 30 Cycloalkylalkyl, C5~C 30 Cycloalkylalkyloxy, C1~C 12 Heterocycline, C1~C 12 Heterocyclyloxy, C1~C 30 Heterocyclylalkyloxy, C1~C 30 Heterocyclylaminyl, C5~C 30 Heterocyclylalkylaminyl, C2~C 12 Heterocyclylcarbonyl, C3~C 30 Heterocyclylalkyl, C1-C 13 Heteroaryl, C3~C 30 Heteroarylalkyl, C2~C 30 Polyethylene glycol, or C3-C 30It is independently selected from one of the polyethylene glycol ethers. In some embodiments, X in the thiophene unit is O.

[0141] A "meta-conjugated linker (MCL)" is any aromatic compound that achieves partial conjugation with two other aromatic compounds (e.g., Ar in the disclosed first type of electrochromic polymer, or another MCL / Ac in the disclosed new type of electrochromic polymer), where partial conjugation occurs when the other two aromatic compounds are linked to the meta position of the arbitrary aromatic compound. The MCL breaks the conjugation between the other two aromatic compounds. The introduction of the MCL results in a polymer having a main chain consisting of aromatic structures, but because the MCL breaks the conjugation and results in partial conjugation, the charge cannot be freely delocalized through the main chain. "Partial conjugation" means that both fully conjugated and unconjugated segments are present. In the case of aromatic structures, "fully conjugated" means that the charge is delocalized and CC bonds and C=C bonds appear alternately. In the case of aromatic structures, "unconjugated" means that the charge cannot be delocalized and the compound is linked to at least one segment by two single bonds (CC) or two multiple bonds (e.g., C=C or triple bonds). "Meta position" refers to the relative position between substituents on the MCL (e.g., another MCL or Ac or Ar disclosed above in the polymer backbone), where the MCL and substituent are bonded / connected in such a way that the MCL and substituent are partially conjugated. "Aromatic moiety" means a cyclic, planar, conjugated moiety with 4n+2π electrons. Benzene units, naphthalene units, fluorene units, pyrrole units, or thiophene units mean units containing benzene, naphthalene, fluorene, pyrrole, thiophene, or their corresponding derivatives. Absorption onset (λc) is a wavelength higher than the wavelength at which the polymer does not exhibit photon absorption. Ac is an aromatic moiety having the structural examples listed above.

[0142] Unlike conventionally reported design strategies in which each MCL is alternately linked to each Ar, the electrochromic polymers of this disclosure allow one MCL to be connected to another. In some embodiments, the novel type of electrochromic polymer disclosed comprises at least two MCLs, e.g., two MCLs, three MCLs, or four MCLs. In some embodiments, the novel type of electrochromic polymer disclosed includes one Ac and at least two MCLs. In some embodiments, the novel type of electrochromic polymer disclosed includes at least one Ac and at least two MCLs. In some embodiments, the total concentration of Ac is less than or equal to the total concentration of MCLs. Due to the fragmentation by more MCLs and direct connections between MCLs, the novel type of electrochromic polymer disclosed contains shorter conjugated segments than the first type of electrochromic polymer discussed earlier, and the conjugation length is significantly reduced, so the absorption of the novel type of electrochromic polymer disclosed is blue-shifted. Accordingly, the novel types of electrochromic polymers disclosed may exhibit a yellow or green color in the oxidized state, or may have at least an absorption peak between 390 and 460 nm, including both ends, in the oxidized state. Furthermore, by adjusting different types of MCL and Ac, the novel design strategies of this disclosure can also produce other colors at longer wavelengths.

[0143] In contrast to conventional conjugated ECPs, which undergo a change from colored to transparent from a neutral to an oxidized state, the disclosed electrochromic polymers undergo a change from transparent to colored from a neutral to an oxidized state. The disclosed electrochromic polymers are transparent in a neutral state and colored and IR absorbent in an oxidized state, a property that is highly desirable for achieving high optical contrast, high transmittance, and synergistic solar heat gain. In some embodiments, the disclosed novel type of electrochromic polymer exhibits high transmittance in a neutral state (e.g., 60% to 99.9%, nearly 100% transparency).

[0144] Despite the high band gap, in some embodiments, by introducing carbazole or carbazole derivative-based MCL, the oxidation potential of the disclosed novel type of electrochromic polymer can be kept relatively low, such as in the range of 0.1 to 1.5 V including both ends, relative to the Ag / AgCl electrode, thereby making the oxidized electrochromic polymer and the corresponding electrochromic element more stable.

[0145] <Example 1: PC-1> In some embodiments, the disclosed PC-1 is [ka] It has the formula.

[0146] PC-1 is synthesized by the following reaction: All starting materials (monomer 1 1 equivalent, monomer 2 0.5 equivalents, monomer 3 0.5 equivalents, N(C4H9)4Cl 1 equivalent, Pd(PPh3) 40.05 equivalents, K2CO3 10 equivalents) are placed in a flask. After replacing the air with N2, 4 ml of degassed water and 10 ml of toluene are added under nitrogen. After refluxing under nitrogen for 60 hours, the reaction mixture is diluted with toluene (5 mL) and washed repeatedly with distilled water. Precipitation is performed with methanol, redissolved in 3-4 mL of chloroform, filtered, and then precipitated with methanol solution. A white solid polymer PC-1 is obtained.

[0147] [ka]

[0148] As shown in the absorbance spectra of the neutral and oxidized states in Figure 11, PC-1 is colorless in the neutral state, with an absorption onset λc of approximately 381 nm and a λmax of approximately 325 nm. When oxidized, PC-1 changes to yellowish-green, and in the oxidized state, it exhibits an absorption peak at approximately 416 nm and another broad absorption band extending to the near-IR region (Figure 11). PC-1 is used as the electrochromic layer, with a mixture of poly(ethylene glycol) diacrylate (PEGDA), 2-hydroxy-2-methylpropiophenone (HMP), and 0.2 M LiClO4 in propylene carbonate (PC) as the electrolyte, and nano-ITO as the ion storage layer to fabricate a solid-state ECD (similar to Figure 10). This solid-state ECD can be stably switched between -0.4 V and 1.75 V at an oxidation potential of approximately 0.63 V (vs. Ag / AgCl) (Figure 12). As shown in Figure 13, the solid-state ECD exhibits high transparency with a transmittance of approximately 82% in the neutral state and approximately 18% in the oxidized state. The corresponding optical contrast of the solid-state ECD is approximately 64%. In an exemplary three-electrode device system using an exemplary PC-1 thin film with 0.2M LiClO4 propylene carbonate as the electrolyte, the PC-1 film exhibits high transparency with a transmittance of approximately 80% in the neutral state and approximately 11% in the oxidized state at a film thickness of 400 nm.

[0149] <Example 2: PC-2> In some embodiments, the disclosed PC-2 is [ka] It has the formula.

[0150] PC-2 is synthesized by the same reaction as PC-1, except that the monomers shown below (1 equivalent, 0.2 equivalents, 0.2 equivalents, 0.1 equivalents, 0.1 equivalents, 0.3 equivalents, and 0.1 equivalents, in the following scheme from left to right) are used.

[0151] [ka]

[0152] As shown in the absorbance spectra of the neutral and oxidized states in Figure 14, PC-2 is colorless in the neutral state, with an absorption onset λc of approximately 400 nm and a λmax of approximately 320 nm. When oxidized, PC-2 changes to a grayish-green color, and in the oxidized state, it exhibits one absorption peak at approximately 410 nm and another broad absorption band extending to the near-IR region. PC-2 is fabricated as a solid-state ECD (similar to Figure 10) using PC-1 as the electrochromic layer, a mixture of poly(ethylene glycol) diacrylate (PEGDA), 2-hydroxy-2-methylpropiophenone (HMP), and 0.2 M LiClO4 in propylene carbonate (PC) as the electrolyte, and nano-ITO as the ion storage layer. This solid-state ECD can stably switch between -0.4 V and 1.8 V at an oxidation potential of approximately 0.35 V (vs. Ag / AgCl) (Figure 15). As shown in Figure 16, the solid-state ECD exhibits high transparency with a transmittance of approximately 93% in the neutral state and approximately 10% in the oxidized state. The corresponding optical contrast of the solid-state ECD is approximately 83%. In an exemplary three-electrode device system using an exemplary PC-2 thin film with 0.2M LiClO4 propylene carbonate as the electrolyte, the PC-2 film exhibits high transparency with a transmittance of approximately 95% in the neutral state and approximately 18% in the oxidized state at a film thickness of 400 nm.

[0153] <Example 3: PC-3> In some embodiments, the disclosed PC-3 is [ka] It has the formula.

[0154] PC-3 is synthesized by the same reaction as PC-1, except that the monomers shown below (from left to right: 1 equivalent, 0.33 equivalents, 0.33 equivalents, and 0.34 equivalents) are used.

[0155] [ka]

[0156] As shown by the absorbance spectra in the neutral and oxidized states, PC-3 is colorless in the neutral state, with an absorption onset λc of approximately 390 nm and a λmax of approximately 305 nm. When oxidized, PC-3 changes to a gravel gray color and shows an absorption peak at approximately 410 nm in the oxidized state. The oxidation potential of the obtained PC-3 is approximately 0.35 V (vs. Ag / AgCl).

[0157] <Example 4: PC-4> In some embodiments, the disclosed PC-4 is [ka] It has the formula.

[0158] PC-4 is synthesized by the same reaction as PC-1, except that the monomers listed below (1 equivalent of each monomer) are used.

[0159] [ka]

[0160] As shown by the absorbance spectra in the neutral and oxidized states, PC-4 is colorless in the neutral state, with an absorption onset λc of approximately 375 nm and a λmax of approximately 305 nm. Upon oxidation, PC-4 changes to green and exhibits absorption peaks at approximately 400 nm and 750 nm in the oxidized state. The oxidation potential of the obtained PC-4 thin film is approximately 0.73 V (vs. Ag / AgCl).

[0161] <Example 5: PC-5> By adjusting the structure of MCL and / or Ac and / or their corresponding ratios, the disclosed novel type of electrochromic polymer may also have an absorption peak wavelength higher than 460 nm in the oxidized state and exhibit a color other than yellow or green. In some embodiments, non-carbazole derivative-based MCL is used in the disclosed novel type of electrochromic polymer. In some embodiments, the disclosed PC-5 is [ka] It has the following formula. PC-5 can be synthesized by a reaction similar to that of PC-1. The PC-5 film is colorless in a neutral state, with an absorption onset λc of approximately 390 nm and a λmax of approximately 330 nm. Upon oxidation, PC-5 changes to orange and exhibits an absorption peak at approximately 490 nm and another broad absorption band extending to the near-IR region. The oxidation potential of the obtained PC-5 is approximately 1.0 V (vs. Ag / AgCl).

[0162] In some embodiments, the novel type of electrochromic polymer disclosed has the following formula:

[0163] [ka]

[0164] (In the formula, n is an integer greater than 1, the sum of α, β, γ, α', β', γ' is equal to 1, 0 < α, β, γ, α', β', and γ' each < 1, and the sum of α', β', γ' is less than or equal to the sum of α, β, γ).

[0165] The disclosed new type of electrochromic polymer can be incorporated into an electrochromic element, for example, as the electrochromic layer 106 in the electrochromic element 100 described above.

[0166] The disclosed electrochromic elements can be used in a variety of applications, including smart windows and glass, biosensors, electronic paper, displays, augmented reality (AR), virtual reality (VR), mixed reality (MR), patterned electrochromic displays, curtain walls, sunroofs, and more. Note that in conventional electrochromic elements, the bleached state (white state) of the element corresponds to the oxidation state of the electrochromic layer. However, in the disclosed electrochromic elements, the bleached state of the element corresponds to the neutral state of the electrochromic layer.

[0167] The preceding descriptions of this disclosure are provided for illustrative and explanatory purposes only. They are not intended to be exhaustive or to limit the disclosure to any specific form of disclosure. The scope and breadth of this disclosure should not be limited by any of the exemplary embodiments described above. Many modifications and changes will be obvious to those skilled in the art. These modifications and changes include any appropriate combination of the features of this disclosure. The embodiments have been selected and described so as to best illustrate the principles and practical applications of this disclosure, and thereby so as to be understandable to those skilled in the art for various embodiments, along with various modifications suitable for specific intended uses. The scope of this disclosure is intended to be defined by the following claims and equivalents. [Explanation of Symbols]

[0168] 100 Electrochromic elements 102 First insulating substrate 104 First conductive layer 106 Electrochromic layer 108 Electrolyte layer 110 Ion storage layer 112 Second conductive layer 114 Second insulating substrate 116 circuits

Claims

1. The following formula: 【Chemistry 1】 (In the formula, MCL represents a meta-conjugated linker, and Ac represents an aromatic moiety; y is a non-negative integer, and n and x are integers greater than 1; a, b, c, d, ..., m, a', b', c', d', ..., m' are the ratios of monomers in the electrochromic polymer; the sum of a, b, c, d, ..., m, a', b', c', d', ..., m' is equal to 1, 0 < a and b < 1, and 0 ≤ c, d, ..., m, a', b', c', d', ..., m' < 1; the sum of a', b', c', d', ..., m' is less than or equal to the sum of a, b, c, d, ..., m; MCL １ , MCL ２ , MCL ３ , MCL ４ , ..., and MCL ｘ Each of these, and its corresponding meta position, is given by the following formula: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 Includes one of the following; Ac １ 、Ac ２ 、Ac ３ 、Ac ４ 、…、Ac ｙ Each of them is 【Chemistry 9】 A unit based on benzene having the formula, or a unit based on naphthalene, or a unit based on fluorene, or a unit based on pyrrole, or a unit based on thiophene, is selected from among these; X is S, Se, N, C, or O; each dashed line represents a position connecting to an adjacent aromatic structure from MCL or Ac; If each of c, d, ..., m, a', b', c', d', ..., m' is equal to 0, then in each MCL, R １ ~R １２ At least one of them is C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Independently selected from one of the polyethylene glycol ethers; When 0 < at least one of c, d, …, m, a', b', c', d', … and m' < 1, in at least one Ac, at least one of R ２１ ~R ３６ and in at least one MCL, at least one of R １ ~R １２ is C １ ~C ３０ alkyl, C ２ ~C ３０ alkenyl, C ２ ~C ３０ alkynyl, C ２ ~C ３０ alkylcarbonyl, C １ ~C ３０ alkoxy, C ３ ~C ３０ alkoxyalkyl, C ２ ~C ３０ alkoxycarbonyl, C ４ ~C ３０ alkoxycarbonylalkyl, C １ ~C ３０ alkylthio, C １ ~C ３０ aminylcarbonyl, C ４ ~C ３０ aminylalkyl, C １ ~C ３０ alkylaminyl, C １ ~C ３０ alkylsulfonyl, C ３ ~C ３０ alkylsulfonylalkyl, C ６ ~C １８ aryl, C ３ ~C １５ cycloalkyl, C ３ ~C ３０ cycloalkylaminyl, C ５ ~C ３０ cycloalkylalkylaminyl, C ５ ~C ３０ cycloalkylalkyl, C ５ ~C ３０ cycloalkylalkyloxy, C １ ~C １２ heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Independently selected from one of the polyethylene glycol ethers; R ２２ ~R ３６ Each of the remaining ones and R ４１ ~R ５３ Each of the remaining ones is hydrogen, C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Independently selected from one of the polyethylene glycol ethers; (It has absorption starting at 420 nm or less in a neutral state, and absorption in visible and / or near-infrared wavelengths in an oxidized state.) An electrochromic polymer comprising [a certain substance].

2. The electrochromic polymer according to claim 1, wherein the electrochromic polymer is colorless in a neutral state.

3. The electrochromic polymer according to claim 1, having at least one absorption peak between 390 and 460 nm, including both ends, in its oxidized state.

4. MCL １ However, the following formula: 【Chemistry 10】 (In the formula, R ２０ C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Selected from one of the polyethylene glycol ethers; each wavy line represents a position of linkage to an adjacent aromatic structure from MCL or Ac. The electrochromic polymer according to claim 1, having the following characteristics.

5. The electrochromic polymer according to claim 1, wherein 0 < a, b, c, a', b', and c' each < 1, and d, ..., m, d', ..., m' each equal to 0.

6. The electrochromic polymer according to claim 1, wherein 0 < a, b, c, a' each < 1, and d, ..., m, b', c', d', ..., m' each equal to 0.

7. Ac １ , Ac ２ , Ac ３ , Ac ４ , ..., Ac ｙ Each of these contains a unit based on thiophene, and the aforementioned thiophene-based unit is given by the following formula: 【Chemistry 11】 (wherein X is S, Se, N, C, or O; R １５ ~R １８ Each of them is hydrogen, C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ (Selected independently from one of the polyethylene glycol ethers) The electrochromic polymer according to claim 1, comprising one of the above.

8. The electrochromic polymer according to claim 7, wherein X in the thiophene-based unit is O.

9. The following formula: 【Chemistry 12】 【Chemistry 13】 (In the formula, n is an integer greater than 1, the sum of α, β, γ, α', β', γ' is equal to 1, 0 < α, β, γ, α', β', and γ' each < 1, and the sum of α', β', γ' is less than or equal to the sum of α, β, γ) The electrochromic polymer according to claim 1, comprising:

10. • First insulating substrate; - A first conductive layer disposed on a first insulating substrate; - An electrochromic layer disposed on a first conductive layer, wherein the following formula is used: 【Chemistry 14】 (In the formula, MCL represents a meta-conjugated linker, and Ac represents an aromatic moiety; y is a non-negative integer, and n and x are integers greater than 1; a, b, c, d, ..., m, a', b', c', d', ..., m' are the ratios of monomers in the electrochromic polymer; the sum of a, b, c, d, ..., m, a', b', c', d', ..., m' is equal to 1, 0 < a and b < 1, and 0 ≤ c, d, ..., m, a', b', c', d', ..., and m' < 1; the sum of a', b', c', d', ..., m' is less than or equal to the sum of a, b, c, d, ..., m; MCL １ , MCL ２ , MCL ３ , MCL ４ , ..., and MCL ｘ Each of these, and its corresponding meta position, is given by the following formula: 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 Includes one of the following; Ac １ , Ac ２ , Ac ３ , Ac ４ , ..., Ac ｙ Each of them is given by the following formula: 【Chemistry 22】 A unit based on benzene, or a unit based on naphthalene, or a unit based on fluorene, or a unit based on pyrrole, or a unit based on thiophene, selected from the above; X is S, Se, N, C, or O; each dashed line represents a position connecting to an adjacent aromatic structure from MCL or Ac; If each of c, d, ..., m, a', b', c', d', ..., m' is equal to 0, then in each MCL, R １ ~R １２ At least one of them is C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Independently selected from one of the polyethylene glycol ethers; If 0 < at least one of c, d, ..., m, a', b', c', d', ... and m' < 1, then in at least one Ac, R ２１ ~R ３６ In at least one of the and at least one MCL, R １ ~R １２ At least one of them is C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Selected from one of the polyethylene glycol ethers; R ２１ ~R ３６ Each of the remaining ones, and R １ ~R １２ Each of the remaining ones is hydrogen, C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Independently selected from one of the polyethylene glycol ethers; and Electrochromic polymers exhibit absorption initiation at 420 nm or below in a neutral state, and absorption in visible and / or near-infrared wavelengths in an oxidized state. An electrochromic layer comprising an electrochromic polymer containing the formula; • Electrolyte layer placed on an electrochromic layer; - A second conductive layer placed on the electrolyte layer; and - A second insulating substrate placed on the second conductive layer; An electrochromic element comprising, An electrochromic element in which the electrochromic layer has a transmittance of 70% to 99.9% at a wavelength of 416 nm in the neutral state of the electrochromic layer.

11. The electrochromic element according to claim 10, wherein the electrochromic layer is colorless in the neutral state of the electrochromic layer.

12. The electrochromic element according to claim 10, having a transmittance of 50% or more at a wavelength of 416 nm when the element is in a white state.

13. The electrochromic element according to claim 10, wherein the electrochromic layer has a transmittance of 95% to 0.1% at a wavelength of 416 nm in the oxidized state of the electrochromic layer.

14. The electrochromic element according to claim 10, having an optical contrast of 50% or more.

15. The electrochromic element according to claim 10, wherein the electrochromic layer has an optical contrast of 50% or more.

16. The electrochromic element according to claim 10, wherein the electrochromic layer has at least one absorption peak between 390 and 460 nm, including both ends, in an oxidized state.

17. MCL １ However, the following formula: 【Chemistry 23】 (In the formula, R ２０ C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ Selected from one of the polyethylene glycol ethers; each wavy line represents a position of linkage to an adjacent aromatic structure from MCL or Ac. An electrochromic element according to claim 10, having the following characteristics.

18. The electrochromic element according to claim 10, wherein 0 < a, b, c, a', b', and c' each < 1, and d, ..., m, d', ..., m' each equal to 0.

19. The electrochromic element according to claim 10, wherein 0 < a, b, c, a' each < 1, and d, ..., m, b', c', d', ..., m' each equal to 0.

20. Ac １ , Ac ２ , Ac ３ , Ac ４ , ..., Ac ｙ Each of these contains a unit based on thiophene, and the aforementioned thiophene-based unit is given by the following formula: 【Chemistry 24】 (wherein X is S, Se, N, C, or O; R １５ ~R １８ Each of them is hydrogen, C １ ~C ３０ Alkyl, C ２ ~C ３０ Alkenil, C ２ ~C ３０ Alkinyl, C ２ ~C ３０ Alkylcarbonyl, C １ ~C ３０ Alkoxy, C ３ ~C ３０ Alkoxyalkyl, C ２ ~C ３０ Alkoxycarbonyl, C ４ ~C ３０ Alkoxycarbonylalkyl, C １ ~C ３０ Alkylthio, C １ ~C ３０ Aminylcarbonyl, C ４ ~C ３０ Aminylalkyl, C １ ~C ３０ Alkyl aminyl, C １ ~C ３０ Alkyl sulfonyl, C ３ ~C ３０ Alkylsulfonylalkyl, C ６ ~C １８ Ariel, C ３ ~C １５ Cycloalkyl, C ３ ~C ３０ Cycloalkylaminyl, C ５ ~C ３０ Cycloalkylalkylaminyl, C ５ ~C ３０ Cycloalkylalkyl, C ５ ~C ３０ Cycloalkylalkyloxy, C １ ~C １２ Heterocyclyl, C １ ~C １２ Heterocyclyloxy, C １ ~C ３０ Heterocyclylalkyloxy, C １ ~C ３０ Heterocyclylaminyl, C ５ ~C ３０ Heterocyclylalkylaminyl, C ２ ~C １２ Heterocyclylcarbonyl, C ３ ~C ３０ Heterocyclylalkyl, C １ ~C １３ Heteroaryl, C ３ ~C ３０ Heteroarylalkyl, C ２ ~C ３０ Polyethylene glycol, or C ３ ~C ３０ (Selected independently from one of the polyethylene glycol ethers) The electrochromic element according to claim 10, comprising one of the above.

21. The electrochromic element according to claim 20, wherein X in the thiophene-based unit is O.

22. Electrochromic polymers are given by the following formula: 【Chemistry 25】 【Chemistry 26】 (In the formula, n is an integer greater than 1, the sum of α, β, γ, α', β', γ' is equal to 1, 0 < α, β, γ, α', β', and γ' each < 1, and the sum of α', β', γ' is less than or equal to the sum of α, β, γ.) The electrochromic element according to claim 10, including the element described in claim 10.

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