Electrochromic compounds, compositions, and optical articles containing the same

Abstract

This invention relates to a novel group of electrochromic compounds. More specifically, it relates to electrochromic polycyclic compounds comprising a five-membered ring, a six-membered ring, or a seven-membered ring, the central core of which contains at least two nitrogen atoms. This invention also relates to the use of these compounds as variable transmittance media for the manufacture of optical articles such as ophthalmic lenses.

Description

[Technical Field]

[0001] The present invention relates to a novel group of electrochromic compounds. More specifically, to electrochromic polycyclic compounds comprising a five-membered ring, a six-membered ring, or a seven-membered ring, the ring having at least two nitrogen atoms in its central core. The present invention also relates to the use of these compounds as variable transmittance media for manufacturing optical articles such as ophthalmic lenses. [Background technology]

[0002] Electrochromism is a well-known physical phenomenon observed in certain classes of compounds whose color reversibly changes when a voltage is applied. These materials exhibit reversible changes in optical properties through oxidation and reduction. Advantageously, electrochromic materials are colorless when no electric field is applied and develop color when an electric field is applied.

[0003] Electrochromic devices, i.e., devices containing electrochromic compounds whose absorbance depends solely on the presence of an electric field, can therefore have two states: a colored state (when electrically activated) and a bleached state (inactive). The light transmission properties of the device depend on the properties of the electrochromic compound.

[0004] When preparing electrochromic compositions used as transparent media for forming high-quality optical articles, particularly high-quality ophthalmic lenses, the selection of the electrochromic compound is crucial. In fact, electrochromic compounds must not only exhibit excellent electrochromic properties such as high absorption of visible light in the colored state, low absorption of visible light in the decolorized state, and rapid coloring and fading rates, but also long-term stability, especially in the presence of oxygen, and excellent solubility in conventional solvents. It is extremely difficult to combine all the required properties into a single compound. Much research has already been conducted to provide electrochromic compounds with an optimal balance. For example, viologen compounds are recognized as particularly interesting due to their high molar extinction coefficients. These molar extinction coefficients are actually higher than those of other electrochromic compounds such as ferrocene and dihydrophenazine derivatives, which are commonly used in electrochromic devices.

[0005] Another problem encountered when using electrochromic compositions in ophthalmic applications is meeting consumer demand for a wide range of available colors, particularly intermediate colors (i.e., brown, gray, gray-green, etc.). Such intermediate colors can preferably be selected based on ISO standard 1836, which defines the relative visual attenuation coefficients of filters of categories 0, 1, 2, and 3. Other examples of shades that define intermediate colors are described in (Patent Document 1) and (Patent Document 2).

[0006] Electrochromic compositions with a desired color can be obtained by mixing different electrochromic compounds. These different electrochromic compounds may include not only oxidizing electrochromic compounds but also reducing electrochromic compounds. However, imparting a desired color to an electrochromic composition is a far more complex task than simply mixing colors. In fact, in addition to the numerous requirements that electrochromic compounds must satisfy, the challenge of using different electrochromic compounds in combination lies in the compatibility of these electrochromic compounds with each other. For example, the absorption coefficients of commonly used electrochromic reducing compounds are usually much lower than those of electrochromic oxidizing compounds such as viologen compounds. On the other hand, when using multiple electrochromic oxidizing compounds in combination in a single composition, it is further necessary that the redox potentials of the electrochromic oxidizing compounds be sufficiently close so that the color changes simultaneously when a potential is applied to the composition. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Patent No. 6,255,238 [Patent Document 2] U.S. Patent No. 5,438,024 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] There is still a need for novel electrochromic materials that can expand the color range from blue to green, red, orange, and yellow using different activation potentials—that is, novel electrochromic materials that can achieve a variety of desired hues without the chameleon effect. [Means for solving the problem]

[0009] As a result of diligent research, the inventors provide novel electrochromic polycyclic compounds comprising a five-membered ring, a six-membered ring, or a seven-membered ring, and containing at least two nitrogen atoms in the central core of the ring. The inventors have found that introducing an azine ring or azine moiety into the structure of conventional electrochromic viologen molecules can yield very interesting results. Such modifications can, for example, lower the absorption wavelength in the visible light region. This is true, for example, in the case of substituted diazines, triazines, and related fused rings.

[0010] Therefore, the present invention relates to an electrochromic compound of formula (I) as defined below. These compounds are advantageous because, - In the inactive state, it is colorless; in the activated state, it is colored, for example, green, red, purple, blue, yellow, or brown; - Reversibly oxidized or reduced; - Easily activated, i.e., with an electrochemical potential of -1.5 to -0.5V; - It is stable, meaning it does not produce degradation products.

[0011] More specifically, the compounds of the present invention exhibit one low reversible reduction peak or two reversible reduction peaks, wherein the two reversible reduction peaks are separated by at least 0.1V, preferably at least 0.3V, more preferably at least 0.4V, and even more preferably at least 0.5V.

[0012] The present invention also relates to an electrochromic composition comprising at least one compound of formula (I).

[0013] Finally, the present invention relates to an electrochromic device, such as an ophthalmic lens, comprising an electrochromic compound or electrochromic composition of formula (I) of the present invention. [Modes for carrying out the invention]

[0014] definition In this specification, the terms "aromatic compound," "aromatic ring," or "heteroaromatic ring" mean an unsaturated compound characterized by one or more planar atomic rings linked by covalent bonds.

[0015] The terms "cyclic compound," "ring compound," or "ring" refer to compounds in which one or more atoms in the compound form a ring. Rings can vary in size from three to many atoms, for example, five, six, or seven atoms, and include examples where all atoms are carbon (i.e., a carbocyclic ring) or where both carbon and non-carbon atoms are present (heterocyclic compounds). More precisely, a "heterocyclic compound or ring structure" is a cyclic compound having atoms of at least two different elements as constituent elements of the ring.

[0016] The term "polycyclic compound" refers to organic compounds characterized by multiple closed rings of atoms, primarily carbon. These ring structures include cycloalkanes, aromatic rings, and other types of rings. They can be three or more atoms in size and have combinations of linkages, such as ligation (biaryls, e.g., biphenyls), condensation (end-to-end, anthracenes and steroids), linkage via one atom (spiro compounds, e.g., spiro compounds), and crosslinking compounds. Examples of polycyclic compounds include bicyclic, tricyclic, and tetracyclic compounds. The term "polycyclic" includes not only polycyclic aromatic compounds (including polycyclic aromatic hydrocarbons) but also heterocyclic aromatic compounds (heteroaromatic compounds are aromatic compounds that contain sulfur, selenium, nitrogen, oxygen, or other non-carbon atoms in addition to carbon in their rings). Polycyclic aromatic hydrocarbons can have rings of various sizes, including non-aromatic ones.

[0017] The term "hydrocarbon" refers to compounds that contain only carbon and hydrogen.

[0018] The term "polycyclic aromatic hydrocarbon" refers to hydrocarbons composed of multiple aromatic rings. This group is a major subset of aromatic hydrocarbons. The simplest such compounds are naphthalene, which has two aromatic rings, as well as anthracene and phenanthrene, which are tricyclic compounds.

[0019] The term "aryl" refers to any monovalent radical of an aromatic hydrocarbon, either monocyclic or polycyclic, containing 6 to 18 carbon atoms, particularly 6 to 10 carbon atoms. 18 Examples of aryl groups include phenyl, naphthyl, anthracenyl, and phenantrenyl. The terms "aryl" and "aromatic hydrocarbon ring" have the same meaning.

[0020] The term "heteroaryl" refers to any monovalent radical of a monocyclic or polycyclic 5-10 membered aromatic group (such as a bicyclic group) containing 1-3 heteroatoms independently selected from oxygen, nitrogen, selenium, and sulfur. Therefore, the term "heteroaryl" includes optionally substituted nitrogen-containing aromatic rings, or optionally substituted bicyclic aromatic rings having two nitrogen atoms. The terms "heteroaryl" and "heteroaromatic ring" have the same meaning. Examples of 5-10 member heteroaryl groups include furyl, thienyl (or thiophen-2-yl or thiophen-3-yl), selenophenyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, isothiazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1-benzofuryl, 1-benzothienyl, indolyl, benzimidazolyl, benzimidazolium, benzimidazoliumylum, indazolyl, 1,2-benzisoxazolyl, and 2,1-benzisoxazoli Examples include 1,2-benzisothiazolyl, 2,1-benzoisothiazolyl, benzothiazolyl, benzoxazolyl, benzoxazoliumyl, benzoselenazolyumyl, benzotriazolyl, pyridinyl, pyridinium, N-alkylpyridinium, N-arylpyridinium, quinolinyl, quinolinium, quinolinium, isoquinolinyl, isoquinolinium, isoquinolinium, pyridadinyl, sinnolinyl, phthalazinyl, pyrimidinyl, quinazolinyl, pyrazinyl, and quinoxalinyl.

[0021] The expression "may be optionally substituted" with respect to groups such as hydrocarbyl groups, alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups (but not limited to these) means that at least one hydrogen in the group may be optionally substituted, including but not limited to halo groups (e.g., F, Cl, I, and Br), hydroxyl groups, ether groups, thiol groups, thioether groups, carboxylic acid groups, carboxylic acid ester groups, phosphate groups, phosphate ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (but not limited to alkyl; alkenyl; alkynyl; cycloalkyl groups including condensed polycyclic cycloalkyl and polycycloalkyl groups; heterocycloalkyl; aryl groups including hydroxysubstituted aryls such as phenol and condensed polycyclic aryls; heteroaryls such as pyridinium or condensed polycyclic heteroaryls; and aralkyl groups), and amine groups, e.g., -N(R) a )(R b )(wherein, R a and R b Each of the above groups is independently replaced or substituted with a group other than hydrogen (selected from hydrogen, hydrocarbyl, and substituted hydrocarbyl).

[0022] In certain embodiments, "may be optionally substituted" means C1-C 18 This means that at least one site selected from the group consisting of alkyl, aryl (substituted or unsubstituted), -CH2-aryl, and heteroaryl (substituted or unsubstituted) is substituted.

[0023] In a particular embodiment, the phrase "may be optionally substituted" means that it is substituted with at least one Y, where Y is C1~C 18 The molecule is an alkyl group, an optionally substituted aryl group, or a -CH2-aryl group.

[0024] In another specific embodiment, the term "optionally substituted aryl" refers to a substituted or unsubstituted aryl moiety, and the moiety is phenyl, naphthyl, biphenyl, halophenyl, C1-C 18 alkylphenyl, C1-C 18 haloalkylphenyl, and C1-C 18 alkoxyphenyl, and is more preferably an aryl moiety selected from the group consisting of phenyl, naphthyl, biphenyl, 1-fluorophenyl, 4-methylphenyl, 1,3-dimethylphenyl, 4-trifluoromethylphenyl, and 4-methoxyphenyl.

[0025] In another specific embodiment, the term "optionally substituted heteroaryl" refers to a substituted or unsubstituted heteroaryl moiety, and the moiety is selected from the group consisting of thienyl (substituted or unsubstituted), pyridiniumyl, N-alkylpyridiniumyl, N-arylpyridiniumyl, N-alkylarylpyridiniumyl, and Z, where Z is

Chemical formula

[0026] More preferably, the thienyl group is thiophen-2-yl or thiophen-3-yl, the N-alkylpyridiniumyl group is the N-hexylpyridiniumyl group, and the N-alkylarylpyridiniumyl is the N-benzylpyridiniumyl group or the N-4-methylphenylpyridiniumyl group.

[0027] In another preferred embodiment, the term “substituted thienyl” group refers to a thienyl group substituted with two N-benzylpyridiniumyl groups.

[0028] The term "hydrocarbyl" refers to a monovalent radical derived from a hydrocarbon.

[0029] "Alkyl" or "C1~C 18 The term "alkyl" refers to any monovalent radical of a linear or branched hydrocarbon chain containing 1 to 18 carbon atoms. The term "C1-C6 alkyl" refers to an alkyl group with 1 to 6 carbon atoms. 18 Examples of alkyl groups include C1-C4 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, or t-butyl, and C6-C alkyl groups such as n-hexyl, n-heptyl, or n-octyl. 18 Examples of alkyl groups include n-pentyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, nonyl, n-decyl, n-undecyl, n-dodecyl, or n-octadecyl groups.

[0030] The term "alkoxy" refers to an alkyl-O- group, where the alkyl is as defined herein. Examples of alkoxy groups include, in particular, methoxy or ethoxy groups.

[0031] The term "Hal" or "halo group" refers to halogen atom substituents such as F, Cl, Br, and I.

[0032] The term "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms, and such alkyl groups are as defined herein. Examples of haloalkyl groups include the trifluoromethyl group (-CF3).

[0033] The expression "arylalkyl" or "aralkyl" refers to any aryl derivative of an alkyl group. In other words, it refers to any monovalent radical induced by replacing one or more hydrogen atoms of an alkyl radical with an aryl group. This refers to a combination of the aryl group and the alkyl group defined above. Examples of arylalkyl groups include benzyl (or CH2-aryl), phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl, naphthylethyl, naphthylpropyl, naphthylbutyl, naphthylpentyl, naphthylhexyl, anthracenylmethyl, anthracenylethyl, anthracenylpropyl, anthracenylbutyl, anthracenylpentyl, anthracenylhexyl, phenantrenylmethyl, phenantrenylethyl, phenantrenylpropyl, phenantrenylbutyl, phenantrenylpentyl, and phenantrenylhexyl.

[0034] The term "pyridinium group," also known as Z in this specification, represents any radical of pyridinium, an aromatic group containing five carbon atoms and a positively charged nitrogen atom. The pyridinium group may be substituted, for example, by Y as shown below: [ka] (In the formula, Y is C1~C 18 (Independently selected from alkyl, optionally substituted aryl, and -CH2-aryl groups).

[0035] The expression "N-alkylpyridinium group" refers to any radical of pyridinium, an aromatic group containing five carbon atoms and a positively charged nitrogen atom, where the nitrogen is substituted with an alkyl group. The N-alkylpyridinium group may be substituted with Y, for example, as shown below: [ka] (In the formula, Y is C1~C 18(Independently selected from alkyl, optionally substituted aryl, and -CH2-aryl groups).

[0036] Preferably, Z is selected from the group consisting of N-hexylpyridiniumyl, N-4-methylphenylpyridiniumyl, and N-benzylpyridiniumyl.

[0037] Electrochromic compounds Thus, the electrochromic compound of the present invention is an electrochromic polycyclic compound represented by formula (I): [ka] (In the formula, A is N, N-R1, or + It is N-R1; B is either C-R2 or N; D is N, N-R4, or + It is N-R4; F may or may not exist, and if it exists, it is -CH2-; R1 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R2 is an aryl that may be optionally substituted with H; R3 is H, C1~C 18 Alkyl, optionally substituted aryl, or optionally substituted heteroaryl, such as Z or -CH2-aryl; R4 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; And / or R5 and R6 together may form an optionally substituted aromatic hydrocarbon ring, e.g., a variant of a condensed ring such as arylene, e.g., benzene, or naphthalene, condensed around the central nitrogen-containing heteroring to which they are bonded, or an optionally substituted heteroaromatic ring, e.g., thiophene, selenofene, pyridine, pyridinium, the aromatic hydrocarbon ring or substituted heteroaromatic ring may be optionally substituted, e.g., with at least one Y or one or two Z; And / or R3 and R4 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridine, pyridinium, pyrimidine, pyrimidinium, pyridazine, pyridazinium, pyrazine, pyrazinium, or an optionally substituted bicyclic aromatic ring containing one or more nitrogen atoms, e.g., quinolinium or benzimidazolium, wherein the aromatic ring is substituted with, for example, at least one Y; And / or R1 and R2 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, condensed around the central nitrogen-containing heteroring to which they are bonded, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; And / or R2 and R3 together may form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted nitrogen-containing nonaromatic ring, e.g., a 7-membered ring, a saturated diazepine, condensed around the central nitrogen-containing heteroring to which they are bonded, wherein the ring is substituted with, for example, at least one Y; Z is [ka] and; Y is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; n is chosen to balance the number of positive charges, and n is at least 2; X is an anion; [ka] It is either a single bond or a double bond; However, the central nitrogen-containing heterocycle contains at least two double bonds; and The electrochromic polycyclic compound includes at least two rings (whether or not they are fused with the central nitrogen-containing heteroring), in addition to the central nitrogen-containing heteroring, provided that at least one of the two rings is a nitrogen-containing ring.

[0038] In the entirety of this invention, unless otherwise specified, Y is advantageously C1~C 18 The Y is an alkyl, optionally substituted aryl, or -CH2-aryl group, for example, Y is methyl, n-hexyl, phenyl, 4-terbutyl, or benzyl.

[0039] In the entirety of this invention, the counterion X -This can be selected from halides, preferably fluorides and chlorides, tetrafluoroborates, tetraphenylborates, hexafluorophosphates, nitrates, methanesulfonates, trifluoromethanesulfonates, p-toluenesulfonates, hexachloroantimonates, bis(trifluoromethanesulfonyl)imides, perchlorates, acetates, and sulfates, or any mixture thereof, preferably X - This is tetrafluoroborate, hexafluorophosphate, or a mixture of both.

[0040] In certain aspects of the present invention, R1 and R2 together form a nitrogen-containing aromatic ring, or a bicyclic aromatic ring comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is condensed with a central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is C1-C6 alkyl or C6-C 10 The compound of formula (I) includes compounds that may be optionally substituted with 1 to 3 Y groups selected from aryl groups, and the aryl groups may be optionally substituted with C1-C6 haloalkyl or C1-C6 alkoxy groups. Examples of Y groups include methyl and phenyl, and the phenyl may be optionally substituted with trifluoromethyl or methoxy.

[0041] In another aspect of the present invention, R3 and R4 together form a nitrogen-containing aromatic ring or a bicyclic aromatic ring containing one or more nitrogen atoms, wherein the aromatic ring is condensed with a central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is C1-C6 alkyl or C6-C 10 The compound of formula (I) may be optionally substituted with 1 to 3 Y groups selected from aryl groups, and the aryl groups may be optionally substituted with C1-C6 haloalkyl or C1-C6 alkoxy groups. In certain embodiments, the nitrogen-containing aromatic ring, or the bicyclic aromatic ring containing one or more nitrogen atoms, is unsubstituted.

[0042] An additional aspect of the present invention is that R2 is H or C6~C 10 It is an aryl, and the C6~C 10 The aryl may be optionally substituted with a C1-C6 alkyl, a C1-C6 haloalkyl, or a C1-C6 alkoxy; in particular the C6-C 10 This includes compounds of formula (I) where the aryl is phenyl.

[0043] An additional aspect of the present invention is that R3 is C6~C 10 Aryl or Z: [ka] C6~C 10 The aryl may be optionally substituted with a C1-C6 alkyl, a C1-C6 haloalkyl, or a C1-C6 alkoxy; in particular the C6-C 10 The aryl is phenyl; Y is C1~C 18 Alkyl or C6-C 10 It is an aryl, and the C6~C 10 The compounds of formula (I) include those in which the aryl group may be optionally substituted with 1 to 3 groups selected from C1 to C6 alkyl groups.

[0044] In another aspect of the present invention, R5 and R6 together form an aromatic hydrocarbon ring or a heteroaromatic ring, the aromatic hydrocarbon ring or heteroaromatic ring being condensed with a central nitrogen-containing heteroaromatic ring to which they are bonded, and the aromatic hydrocarbon ring or heteroaromatic ring having one or two Z: [ka] It may be optionally substituted, and Y is -CH2-(C6~C 10The compounds of formula (I), such as aryls, for example benzyl, are included. For example, R5 and R6 may together form an aromatic hydrocarbon ring, such as aryls, such as phenyls, or a heteroaromatic ring, such as thiophene or selenofene, which are condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and the aromatic hydrocarbon ring or heteroaromatic ring may have one or two Zs: [ka] It may be optionally substituted, and Y is -CH2-(C6~C 10 Aryl, for example, benzyl.

[0045] In an additional aspect of the present invention, R5 is H, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 The compounds of formula (1) include an aryl or a 5- to 10-membered heteroaryl, wherein the aryl or heteroaryl may be optionally substituted with 1 to 3 groups selected from Hal, C1-C6 alkyl, or C1-C6 haloalkyl. For example, R5 can be selected from H, methyl, thienyl, or phenyl which may be optionally substituted with Hal (e.g., F).

[0046] In an additional aspect of the present invention, R6 is H, C6~C 10 It is an aryl, and the aryl is a 1-C6 alkyl, C1-C6 haloalkyl, or C6-C 10 It is optionally substituted with 1 to 3 groups selected from the aryl group, or R6 is Z: [ka] And, Y is C1~C 18 Alkyl, C6~C 10The compounds of formula (1) include an aryl group, wherein the aryl group may be optionally substituted with 1 to 3 groups selected from C1 to C6 alkyl groups. For example, R6 can be selected from H, naphthyl, or phenyl, wherein the phenyl group may be optionally substituted with phenyl, methyl, and / or trifluoromethyl, or R6 can be selected from Z, where Y is n-hexyl or tolyl.

[0047] In certain aspects of the present invention, the compound of the present invention is an electrochromic polycyclic compound of formula (I): [ka] (In the formula, A is N, N-R1 or + It is N-R1; B is either C-R2 or N; D is N, N-R4 or + It is N-R4; F may or may not exist, and if it exists, it is -CH2-; R3 is H, an aryl which may be optionally substituted, or a heteroaryl which may be optionally substituted, such as Z; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; And / or R5 and R6 together may form an optionally substituted aromatic hydrocarbon ring, such as a modified form of a condensed ring, such as arylene, such as benzene, or such naphthalene, or an optionally substituted heteroaromatic ring, which is condensed around the central nitrogen-containing heteroring to which they are bonded, and the aromatic hydrocarbon ring or substituted heteroaromatic ring may be optionally substituted, for example, with at least one Y, one Z, or two Z; And / or D is N-R4 or + In the case of N-R4, R3 and R4 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridine, pyridinium, pyrimidine, pyrimidinium, pyridazine, pyridazinium, pyrazine, pyrazinium, or an optionally substituted bicyclic aromatic ring containing one or more nitrogen atoms, e.g., quinolinium or benzimidazolium, wherein the aromatic ring is substituted with, for example, at least one Y; And / or A is N-R1 or + In the case of N-R1, R1 and R2 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, condensed around the central nitrogen-containing heteroring to which they are bonded, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; And / or R2 and R3 together may form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted nitrogen-containing nonaromatic ring, e.g., a 7-membered ring, a saturated diazepine, condensed around the central nitrogen-containing heteroring to which they are bonded, wherein the ring is substituted with, for example, at least one Y; Z is [ka] And, Y is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; n is chosen to balance the number of positive charges, and n is at least 2; X is an anion; [ka] It is either a single bond or a double bond; However, the central nitrogen-containing heterocycle contains at least two double bonds; and The electrochromic polycyclic compound includes at least two rings (whether or not they are fused with the central nitrogen-containing heteroring), in addition to the central nitrogen-containing heteroring, provided that at least one of the two rings is a nitrogen-containing ring.

[0048] In some specific aspects of the present invention, D is + If it is N-R4, then B is C-R2, and A is + It is N-R1: - R3 and R4 together form a pyridinium or optionally substituted benzimidazolium ring condensed around the central nitrogen-containing heteroring to which they are bonded; - R1 and R2 together form a pyridinium, optionally substituted quinolinium, optionally substituted benzimidazolium, or optionally substituted benzothiazolium, condensed around the central nitrogen-containing heteroring to which they are joined.

[0049] In another specific embodiment of the present invention, D is + If it is N-R4, then B is C-R2, and A is + It is N-R1: - R3 and R4 together form a pyridinium or N-methyl-benzimidazolium ring, condensed around the central nitrogen-containing heteroring to which they are bonded; - R1 and R2 together form a pyridinium, quinolinium, phenyl-substituted quinolinium, alkoxyphenyl-substituted quinolinium, haloalkylphenyl-substituted quinolinium, benzothiazolium, or optionally N-alkyl-substituted benzimidazolium ring, condensed around the central nitrogen-containing heteroring to which they are bonded; more preferably, alkoxyphenyl-substituted quinolinium is 4-[4-methoxyphenyl)-quinolinium], haloalkylphenyl-substituted quinolinium is 4-[4-trifluoromethylphenyl)-quinolinium], and N-alkyl-substituted benzimidazolium is N-methylbenzimidazolium; When R3 and R4 combine to form a benzimidazolium ring, and when R1 and R2 combine to form a benzimidazolium ring, R2 and R3 combine to form a saturated diazepine condensed around the central nitrogen-containing heteroring to which they are joined.

[0050] In a first modified form of the present invention, the compound of the present invention is an electrochromic polycyclic compound having a nitrogen-containing six-membered heterocycle at its center and represented by formula (II): [ka] (In the formula, A is N or+ It is N-R1; B is either C-R2 or N; D is N or + It is N-R4; R1 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R2 is an aryl that may be optionally substituted with H; R3 is H, C1~C 18 Alkyl, optionally substituted aryl, or optionally substituted heteroaryl, such as Z or -CH2-aryl; R4 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; And / or R5 and R6 together may form an optionally substituted aromatic hydrocarbon ring, e.g., arylene, e.g., benzene, or an optionally substituted heteroaromatic ring, e.g., thiophene, selenofene, pyridine, pyridinium, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and the aromatic hydrocarbon ring or heteroaromatic ring may be optionally substituted, e.g., with at least one Y or one or two Z; And / or R3 and R4 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium or benzimidazolium, containing one or more nitrogen atoms, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, the aromatic ring being, for example, substituted with at least one Y, and for example, substituted with an optionally substituted aryl; And / or R1 and R2 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; And / or R2 and R3 together may form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, fused to the central nitrogen-containing six-membered heteroring to which they are bonded, but substituted with at least Y; However, the electrochromic polycyclic compound includes at least two rings in addition to the central nitrogen-containing six-membered heteroring (whether or not it is fused to the central nitrogen-containing six-membered heteroring), and at least one of the two rings is a nitrogen-containing ring; Z, Y, n, and X are as defined above.

[0051] In one embodiment of this first variant, the compound of formula (II) is A + N is R1; D is +It is an N-R4 pyridinium ring in which R3 and R4 are fused together to form a central nitrogen-containing six-membered heteroring, which is represented by formula (III): [ka] (In the formula, B is C-R2; R1 and R2 together form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, C1~C 18 The alkyl, optionally substituted aryl, optionally substituted heteroaryl, or Z; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; Z, Y, [ka] (where n and X are as defined above).

[0052] According to this particular embodiment, the compound may be a compound represented by formula (IIIa), (IIIb), (IIIc), or (IIId): [ka] (In these formulas, R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, C1~C 18 The alkyl, optionally substituted aryl, optionally substituted heteroaryl, or Z; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; W is NY, S, O, or Se; Z, Y, [ka] (where n and X are as defined above).

[0053] Preferred compounds include those in which R5 is H, C1-C6 alkyl, C1-C6 alkoxy, or optionally substituted with C6-C 18 R5 is an aryl, optionally substituted five-membered heteroaryl, or optionally substituted six-membered heteroaryl; preferably R5 is H, C1-C3 alkyl, optionally substituted C6 aryl, or an unsubstituted five-membered heteroaryl; more preferably R5 is H, methyl, phenyl, naphthyl (such as naphthalene-2-yl), substituted phenyl (such as 2-fluorophenyl, 4-(trifluoromethyl)phenyl, 2,4-(dimethylphenyl)), or an unsubstituted five-membered heteroaryl having one heteroatom, such as thiophene-2-yl or thiophene-3-yl; R6 is also H, C1-C6 alkyl, or optionally substituted C6-C 18R6 is an aryl, optionally substituted five-membered heteroaryl, or optionally substituted six-membered heteroaryl; preferably R6 is H, C1-C3 alkyl, optionally substituted C6 aryl, or an unsubstituted five-membered heteroaryl; more preferably R6 is H, methyl, phenyl, naphthyl (e.g., naphthalene-2-yl), substituted phenyl (e.g., 2-fluorophenyl, 4-(trifluoromethyl)phenyl, 2,4-(dimethylphenyl)), or an unsubstituted five-membered heteroaryl having one heteroatom, e.g., thiophene-2-yl or thiophene-3-yl; n is 2; X - However, it can be a tetrafluoroborate or hexafluorophosphate, preferably a tetrafluoroborate, of formula (IIIa).

[0054] A preferred compound is one in which R5 and R6 are H; Y is an optionally substituted aryl, and Y is preferably an optionally substituted phenyl, more preferably Y is phenyl, 4-methoxyphenyl, or 4-(trifluoromethyl)phenyl; n is 2; X - However, it may be a tetrafluoroborate or hexafluorophosphate, preferably a tetrafluoroborate, of formula (IIIb) or formula (IIIc).

[0055] Preferred compounds are W is S or NY, and Y is C1~C 18 It is an alkyl group, where Y is preferably a C1-C6 alkyl group, and more preferably Y is a C1-C4 alkyl group, such as methyl; R5 may be H, C1-C6 alkyl, C1-C6 alkoxy, or optionally substituted with C6-C 18Aryl, optionally substituted 5-membered heteroaryl, or optionally substituted 6-membered heteroaryl; preferably, R5 is H, C1-C3 alkyl, optionally substituted C6 aryl, or unsubstituted 5-membered heteroaryl; more preferably, R5 is H, methyl, phenyl, naphthyl (such as naphthalene-2-yl), substituted phenyl (such as 2-fluoro-phenyl, 4-(trifluoromethyl)phenyl, 2,4-(dimethylphenyl)), unsubstituted 5-membered heteroaryl having one heteroatom, such as thiophene-2-yl or thiophene-3-yl; R6 is also H, C1-C6 alkyl, optionally substituted C6-C 18 Aryl, optionally substituted 5-membered heteroaryl, or optionally substituted 6-membered heteroaryl; preferably, R6 is H, C1-C3 alkyl, optionally substituted C6 aryl, or unsubstituted 5-membered heteroaryl; more preferably, R6 is H, methyl, phenyl, naphthyl (such as naphthalene-2-yl), substituted phenyl (such as 2-fluoro-phenyl, 4-(trifluoromethyl)phenyl, 2,4-(dimethylphenyl)), unsubstituted 5-membered heteroaryl having one heteroatom, such as thiophene-2-yl or thiophene-3-yl; [Chemical formula] is a single bond or a double bond, preferably a single bond, n is 2; X - is tetrafluoroborate or hexafluorophosphate, preferably tetrafluoroborate, and can be of formula (IIId).

[0056] In the second embodiment of this specific first variant form, the compound of formula (II) is such that A is N ; D is N, and this is represented by formula (IV): [Chemical formula] (wherein, B is either C-R2 or N; R2 is H or an optionally substituted aryl; preferably H or phenyl; R3 is an aryl or Z which may be optionally substituted; R5 is H; R6 is Z; Alternatively, R5 and R6 may together form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, e.g., arylene, e.g., benzene, which is fused to the central nitrogen-containing six-membered heteroring to which they are bonded, and the heteroaromatic ring or aromatic hydrocarbon ring is substituted with, for example, at least Y or, for example, two Z; Y, Z, n, and X are as defined above.

[0057] According to this embodiment, R5 and R6 may together form an optionally substituted aromatic hydrocarbon ring, e.g., aryl, e.g., benzene, or an optionally substituted heteroaromatic ring, e.g., thiophene, selenofene, which is condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and which may be optionally substituted with, for example, at least one Y, one Z, or two Zs, and can be represented as follows: [ka] (In these equations, B, R3, Z, and Y are as defined above.)

[0058] In a preferred embodiment, R5 and R6 together form a thiophene condensed on a central nitrogen-containing six-membered heteroring to which they are bonded, the thiophene ring being substituted with one or two Z groups, and more preferably, the thiophene ring being substituted with two N-benzylpyridinium groups.

[0059] Therefore, according to this particular embodiment, the compound may be of formula (V). [ka] (B is CH or N; preferably CH; Z, Y, and X are as defined above).

[0060] Preferred compounds of formula (V) are such that Y is a C1-C8 alkyl, optionally substituted aryl, or -CH2-aryl; preferably Y is methyl, n-hexyl, benzyl, phenyl, or p-tolyl; n is 2; X - However, Y may be tetrafluoroborate or hexafluorophosphate, preferably hexafluorophosphate. More preferably, Y is hexyl, 4-methylphenyl, or benzyl.

[0061] Other preferred compounds according to this particular embodiment are typically compounds of formula (VI) or (VII). [ka] (In these formulas, R2 is an aryl that may be optionally substituted with H; R3 is H, an aryl, or Z which may be optionally substituted; Z, Y, n, and X are as defined above.

[0062] Preferred compounds of formulas (VI) and (VII) are an aryl (e.g., phenyl) whose R2 may be optionally substituted; R3 may also be an aryl (e.g., phenyl) whose R3 may also be optionally substituted; Y is a C1-C8 alkyl, an optionally substituted aryl, or a -CH2 aryl; preferably Y is methyl, n-hexyl, benzyl, phenyl, or p-tolyl; n is 2; X - The compound is a tetrafluoroborate or a hexafluorophosphate, preferably a hexafluorophosphate.

[0063] In the third embodiment of this first variant, the compound of formula (II) is A + It is a compound in which N-R1 and B is C-R2, and this is represented by formula (III'). [ka] (In the formula, R1 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; D is N or + It is N-R4; R4 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R5 and R6 together form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and which is, for example, substituted with at least one Y; R2 and R3 together form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and which is, for example, substituted with at least one Y; And / or R1 and R6 together may form an optionally substituted nitrogen-containing six-membered ring condensed around the central nitrogen-containing six-membered heteroring to which they are joined; Y, n, and X are as defined above.

[0064] According to this third embodiment, the compound may be, for example, pyrido[2,3-b]quinoxaline, pyrido[3,4-b]quinoxaline, pyrido[2,3-b]thieno[3,4-e]pyrazine, or pyrido[3,4-b]thieno[3,4-e]pyrazine.

[0065] Therefore, according to this third embodiment, the compound of the present invention can be a compound of formula (III') in which R2 and R3 together form an optionally substituted aromatic hydrocarbon ring, for example, a six-membered ring, for example, benzene, substituted with, for example, at least one Y, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded; D is N; and R5 and R6 together form an optionally substituted heteroaromatic ring, for example, pyridinium, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, substituted with, for example, at least one Y. These compounds can be expressed as follows: [ka] (In these equations, R1, Y, X, and n are as defined above.)

[0066] Furthermore, according to this third embodiment, the compound of the present invention is a compound of formula (III') wherein R2 and R3 together form an optionally substituted aromatic hydrocarbon ring, for example, a six-membered ring, such as benzene, fused with, for example, at least one Y, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded; D is N; R5 and R6 together form an optionally substituted heteroaromatic ring, for example, pyridinium, fused with, for example, at least one Y, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded; and R1 and R6 together form an optionally substituted nitrogen-containing six-membered ring, fused around the central nitrogen-containing six-membered heteroring to which they are bonded. These compounds can be expressed as follows: [ka] (In the formula, R1, Y, X, and n are as defined above.)

[0067] The compounds of the present invention may be compounds of formula (III'), wherein R2 and R3 are fused together to an optionally substituted heteroaromatic ring, a 5-membered ring, or a sulfur-containing aromatic ring, such as thiophene, which is substituted with, for example, at least one Y; D is N; and R5 and R6 are fused together to an optionally substituted heteroaromatic ring, such as pyridinium, which is substituted with, for example, at least one Y, or a sulfur-containing aromatic ring, such as pyridinium, which is fused together to an optionally substituted heteroaromatic ring, such as pyridinium, which is substituted with, for example, at least one Y. These compounds can be expressed as follows: [ka] (In the formula, R1, Y, X, and n are as defined above.)

[0068] The compounds of the present invention may be compounds of formula (III') wherein R2 and R3 are fused together to an optionally substituted heteroaromatic ring, a 5-membered ring, or a sulfur-containing aromatic ring, such as thiophene, which is substituted with at least one Y; D is N; R5 and R6 are fused together to an optionally substituted heteroaromatic ring, such as pyridinium, which is substituted with at least one Y, or a sulfur-containing aromatic ring, such as pyridinium, which is substituted with at least one Y; and R1 and R6 are fused together to an optionally substituted nitrogen-containing 6-membered ring, which is fused with at least one Y. These compounds can be expressed as follows: [ka] (In the formula, R1, Y, X, and n are as defined above.)

[0069] The compounds of the present invention are such that R2 and R3 together form an optionally substituted heteroaromatic ring, 5-membered ring; sulfur-containing aromatic ring, such as thiophene, which is condensed to the central nitrogen-containing 6-membered heterocycle to which they are attached, and is substituted, for example, with at least one Y; D is + N-R4; R5 and R6 together form an optionally substituted heteroaromatic ring, such as pyridinium, which is condensed to the central nitrogen-containing 6-membered heterocycle to which they are attached, and is substituted, for example, with at least one Y. The compound of formula (III') may also be used. These compounds can be represented as follows: [Chemical formula] (wherein R1, R 4、 Y, X, and n are as defined above).

[0070] In a second variant of the present invention, the compounds of the present invention are of formula (IX) having a central nitrogen-containing 7-membered heterocycle [Chemical formula] (wherein B is C-R2; R3 and R4 together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium or benzimidazolium, which is condensed to the central nitrogen-containing 7-membered heterocycle to which they are attached, and the aromatic ring is substituted, for example, with at least one Y, and preferably the aromatic ring is unsubstituted; R1 and R2 together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, quinolinium, or benzimidazolium, which is condensed to the central nitrogen-containing 7-membered heterocycle to which they are attached, and is substituted, for example, with an optionally substituted aryl; R2 and R3 may together form an optionally substituted nitrogen-containing non-aromatic ring, such as a 7-membered ring or saturated diazepine, condensed around the central nitrogen-containing 7-membered heteroring to which they are joined, and the non-aromatic ring is preferably unsubstituted; Y, n, and X are as defined above.

[0071] In a particularly preferred embodiment of the present invention, the compound of formula (I) is selected from the group consisting of the following:

[0072] [Table 1]

[0073] [Table 2]

[0074] [Table 3]

[0075] [Table 4]

[0076] The compound represented by formula (I) can be prepared according to various methods well known in the art.

[0077] For example, the compound represented by formula (I) can be obtained according to the synthetic route detailed below.

[0078] 2,5-dibromopyrazine (RCEllingson and RLHenry, J.Am.Chem.Soc., 1949, 71, 2798; A.-M.Stadler, F.Funtoriero, F.Nastasi, S.Campagna and J.-M.Lehn, Chem.Eur.J., 2010, 16, 5645) was coupled with 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine via Suzuki-Miyaura coupling to obtain 2,5-bis(4-pyridyl)pyrazine (International Publication No. 2016 / 14753 pamphlet) in good yield. Subsequent conversion to bispyridinium derivatives was achieved by alkylation with iodoalkane or conversion to an N,N'-bis(2,4-dinitrophenyl) salt followed by substitution with an aromatic amine (Scheme 1). [ka]

[0079] An overview exists regarding the synthetic route and chemistry of 1,2,4-triazines (SARaw and RJKTaylor, Adv. Heterocycl. Chem., 2010, 100, 75). Compounds such as 3,6-diaryl-1,2,4-triazines are often prepared by condensation of amidorazone and a 1,2-dicarbonyl compound, and various variations of this procedure have been developed. The 1,2,4-triazine with a pyridyl group attached at the 2nd position (J. Sauer, DK Heldmann, GRPabst, Eur. J. Org. Chem., 1999, 313) has been reported, and the reactions of 3,6-bis(2-pyridyl)- and 3,6-bis(4-pyridyl)-1,2,4-triazine have also been reported (M. Takahashi, Y. Hikita, M. Fukui, Heterocycles, 1989, 29, 1379), but the synthesis of the latter had not been reported until now. The procedure used in this study is based on the synthesis method for 6-aryl-3-pyridyl-1,2,4-triazine from oxyminohydrazone (VNKozhevnikov, OV Shabunina, DSKopchuk, MMUstinove, B. Koenig and DNKozhennikov, Tetrahedron, 2008, 64, 8963). Therefore, 4-acetylpyridine was converted to 2-hydrazinylidene-2-(4-pyridyl)acetaldehyde oxime according to the procedure in the literature (VNKozhevnikov, DNKozhennikov, OVShabunina, VLRusinov and ONChupakhin, Tetrahedron Lett., 2005, 46, 1791), and 3,6-bis(4-pyridyl)-1,2,4-triazine was obtained in good yield by condensation with pyridine-4-carboxyaldehyde. Subsequent N-alkylation proceeded readily (Scheme 2). [ka]

[0080] 6-substituted and 6,7-disubstituted dipyrids [1,2-a:2',1'-c]pyrazine-5,8-diium are obtained by alkylating 2,2'-bipyridine with a suitable α-haloketone, followed by dehydration and cyclization of the resulting bipyridinium salt with phosphorus tribromide according to the methods described in the literature (DHCorr and EEGlover, J. Chem. Soc., 1965, 5816; ICCalder and WHFSasse, Aust. J. Chem., 1968, 21, 2951; ALBlack and LASummers, J. Heterocycl. Chem., 1971, 8, 29). The resulting dibromide is stable in itself, but can be conveniently used to produce various salts by anion exchange. The procedure is shown in Scheme 3. [ka]

[0081] Electrochromic composition The present invention also relates to an electrochromic composition comprising at least one compound of formula (I) as defined above as an oxidizing electrochromic compound, and a host medium. One or more additional oxidizing electrochromic compounds can be added to the composition of the present invention to adapt the intensity of the color or coloring state of the composition of the present invention. The additional compounds may be other compounds of formula (I) or other compounds such as compatible dyes or pigments. For example, the additional oxidizing electrochromic compounds can be selected from alkyl viologens, aryl viologens, alkylaryl viologens, anthraquinones, benzazoles, imidazo[1,2-α]pyridines, 2,1,3-benzothiadiazoles, imidazoles, benzoserenadiazoles, benzoserenazoles, and derivatives. Preferably, the additional compounds have an oxidation-reduction potential close to that of the compounds of formula (I).

[0082] The composition may also contain at least one reducing compound. The reducing compound may also be an electrochromic compound. Examples of reducing compounds include 5,10-dihydrophenazine, phenothiazine, phenoxazine, N,N,N',N'-tetramethyl-p-phenylenediamine, thioanthrene, tetrathiafulvalene, ferrocene, and their derivatives.

[0083] The compositions of the present invention may include a host medium, which may be a fluid, a liquid crystalline medium, or a gel. The host medium is introduced into the composition of the present invention to dissolve the electrochromic compound. The host medium is preferably selected from the group consisting of organic solvents, liquid crystals, polymers, liquid crystalline polymers, and mixtures thereof.

[0084] Suitable organic solvents that can be used as host media are redox-compatible solvents that do not react with the electrochromic compound of the composition, such as ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, acetonitrile, propionitrile, benzonitrile, glutaronitrile, methylglutaronitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane, benzene, toluene, methyl ethyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, 2-methoxyethyl ether, xylene, cyclohexane, 3-methylcyclohexanone, ethyl acetate, ethyl phenylacetate, tetrahydrofuran, methanol, methyl propionate, ethylene glycol, ethylene carbonate, ionic liquids, and mixtures thereof. Carbonates, particularly propylene carbonate, are preferred.

[0085] Suitable examples of liquid crystals that can be used as host media include nematic media or chiral nematic media.

[0086] Suitable polymers that can be used as host media include solvent-soluble polymers, particularly PMMA or other acrylate polymers, polyurethanes, polyethylene oxide, polypropylene oxide, polyvinyl acetate, poly(N-vinylpyrrolidone), and polyvinylidene fluoride.

[0087] Suitable liquid crystal polymers that can be used as host media include Merck RM257 (Merck), LC242 (BASF), or SLM90519 (Wacker). These liquid crystal polymers are generally used in combination with organic solvents, such as one of the above-mentioned organic solvents.

[0088] Electrochromic devices The present invention also relates to electrochromic devices comprising a compound or composition of formula (I) of the present invention. The device can be selected from optical articles; preferably optical lenses or optical filters; windows, preferably aircraft or automobile windows; visors, mirrors, variable transmittance devices, and display elements or devices, particularly segment displays or matrix displays. Preferably, the device of the present invention is an optical article, more preferably an optical lens, and even more preferably an ophthalmic lens.

[0089] Non-limiting examples of ophthalmic lenses include corrective and non-corrective lenses (which may or may not be segmented), including monofocal or multifocal lenses, as well as other optical articles used to correct, protect, or enhance vision, such as contact lenses, intraocular lenses, sunglasses, ski goggles, magnifying lenses, filters, protective lenses, and visors, e.g., motorcycle visors and helmets. Non-limiting examples of display elements and devices include screens and monitors. Non-limiting examples of windows include windows of automobiles, ships, aircraft, or buildings. Variable transmittance devices include, but are not limited to, optical articles that can rapidly change between a high transmittance (or "transparent") state and a low transmittance (or "dark") state, such as contact lenses, intraocular lenses, sunglasses, ski goggles, magnifying lenses, filters, protective lenses, and visors, e.g., motorcycle visors and helmets. The optical switches used herein are variable transmittance devices that have a high transmittance (or "transparent") state and a low transmittance (or "dark") state and are used to control the transmittance state of larger devices.

[0090] Preferably, the device of the present invention includes a mechanism for holding the compound or composition of the present invention in a mechanically stable environment. More preferably, the device may consist of a pair of opposing substrates having a gap for receiving a mixture of a host medium and the compound or composition of the present invention, and a frame for holding the pair of substrates adjacent to each other.

[0091] Accordingly, the device of the present invention can constitute an optical component comprising at least one array of transparent cells arranged parallel to its surface, as disclosed in International Publication No. 2006 / 013250, each cell being sealed and containing at least one compound or composition of the present invention.

[0092] Another device according to the present invention may be the device described in French Patent No. 2937154 or French Patent No. 2950710, which comprises at least one compound or composition of the present invention.

[0093] The present invention can be further illustrated by the following non-limiting embodiments, which are provided for illustrative purposes only and do not limit the scope of the appended claims.

[0094] Synthesis of the Compound of the Present Invention 6-Phenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) Compound 1 [ka] 6-Phenyldipyride[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (1.5 g, 3.58 mmol) (prepared according to DHCorr and EEGlover, J. Chem. Soc., 1965, 5816) was dissolved in a small amount of water and added dropwise with stirring to a solution of NaBF4 (2.36 g, 21.5 mmol) in water (70 mL) to obtain a dark solution. After 2 hours, another 1.00 g, 9.1 mmol of NaBF4 was added, and stirring was continued until the precipitation of the product was complete (approximately 4 hours). The product was separated by filtration, washed with the filtrate, a small amount of water, then diethyl ether, and air-dried. The title compound (0.80 g, 52%) was obtained as a purple microcrystalline powder;δ H [(CD3)2CO, 400MHz] 7.78-7.90 (3H,m), 7.93-7.99 (2H,m), 8.81 (1H,dt,J=1.3 and 6.8Hz), 8.96 (1H,dt,J=1.2 and 6.4Hz), 9.32-9.40 (2H,m), 9.50 (1H,s), 9.64 (1H,dd,J=0.9 and 6.6Hz), 9.89 (1H,bd,J=6.6Hz) and 10.04-10.14 (2H,m); δ F [(CD3)2CO,376MHz] -151.69,-151.64;δ C(DMSO-d6, 100 MHz) 126.34, 126.62, 126.75, 127.10, 130.69, 130.98, 131.05, 131.23, 132.99, 135.81, 137.56, 138.65, 139.96, 142.00, 146.91 and 146.9

[0095] 1-[2-(Naphthalen-2-yl)-2-oxoethyl]-[2,2'-bipyridine]-1-ium bromide

Chem.

[0096] 6-(Naphthalen-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide

Chem.

[0097] 6-(naphthalene-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 2 [ka] A solution of 6-(naphthalene-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium bromide (1.50 g, 3.2 mmol) in water (40 mL) was added dropwise to a solution of NaBF4 (3.53 g, 21.1 mmol) in water (100 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (10 mL), and air-dried. The resulting powder was extracted with acetone (6 × 100 mL), and the solvent was reduced at 40°C (approximately 100 mL). By filtering the residue, the title compound (0.80 g, yield 52%) was obtained as an ochre powder;δ H [(CD3)2CO,400MHz] 7.75-7.86(2H,m),7.97(1H,dd,J=1.8 and 8.5Hz),8.13-8.22(2H,m),8.35(1H,ap p.d,J=8.5Hz),8.59(1H,bs),8.81(1H,app.dt.J=1 and 7.7Hz),8.98(1H,app.dt, J=1.0 and 7.7Hz),9.34-9.43(2H,m),9.59(1H,s),9.77(1H,app.d,J=6Hz),9.91( 1H,app.d,J=6.2Hz),10.09(1H,app.d,J=8.6Hz) and 10.14(1H,app.d,J=8.4Hz);δ F [(CD3)2CO,376MHz] -152.16,152.11;δ C [(CD3)2CO, 100MHz] 123.65, 124.46, 125.83, 126.54, 127.00, 127.33, 127.88, 128.21, 128.88, 128.98, 130.21, 130.96, 132.28, 133.23, 134.80, 136.72, 137.93, 138.80, 140.12, 142.19, 146.71 and 146.81.

[0098] 1-{2-([1,1'-biphenyl]-4-yl)-2-oxoethyl}-[2,2'-bipyridine]-1-ium bromide [ka] A mixture of 2,2'-bipyridine (2 g, 12.8 mmol) and 1-([1,1'-biphenyl]-4-yl)-2-bromoethane-1-one (3.65 g, 13.3 mmol) was heated at 100°C for 45 minutes. The resulting solid was cooled, crystallized twice from EtOH / Et2O, and air-dried to obtain the title compound (4.64 g, yield 84%) as a pale yellowish-brown powder;δ H (CD3OD,400MHz)6.51(2H,s),7.41-7.63(4H,m),7.72-7.79(2H,m),7.88(2H,d,8.3Hz),8.04-8.17(4H,m),8.33(1H,app.t ,J=6.7Hz),8.40(1H,app.d,J=4.5Hz),8.50(1H,app.d,J=8Hz),8.87(1H,app.dt,J=0.7 and 8Hz) and 9.14(1H,app.d,J=6Hz);δ C (CD3OD, 100MHz) 63.34, 124.74, 125.16, 125.63, 125.79, 125.97, 127.09, 127.39, 127.55, 128.59, 130.93, 137.18, 137.98, 145.66, 145.79, 147.75, 147.77, 148.22, and 187.96.

[0099] 6-([1,1'-biphenyl]-4-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A mixture of 1-{2-([1,1'-biphenyl]-4-yl)-2-oxoethyl}-[2,2'-bipyridine]-1-ium bromide (3.23 g, 7.5 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes, cooled, and the residue was filtered off. The mixture was washed with Et2O (3 × 50 mL) and crystallized from MeOH. The solution was diluted with diisopropyl ether and filtered. The combined solid was recrystallized from MeOH at high temperature, washed with Et2O (20 mL), and vacuum dried to obtain the title compound (1.57 g, 42%) as a green / yellow powder;δ H(D2O,400MHz)7.37-7.44(1H,m),7.45-7.51(2H,m),7.70-7.79(4H,m),7.96(2H,d,J=8.2Hz),8.49(1H,app.t,J=7.1Hz),8. 61(1H,app.d,J=6.9Hz),9.03-9.10(2H,m),9.16(1H,s),9.44-9.51(2H,m),9.68(1H,d,J=8.7Hz) and 9.73(1H,d,J=8.4Hz);δ C (D2O, 100MHz) 124.02, 126.05, 126.46, 127.12, 127.27, 128.66, 128.83, 129.33, 130.80, 130.94, 131.00, 136.47, 136.86, 137.88, 138.95, 139.81, 141.77, 145.01, 146.81 and 147.03.

[0100] 6-([1,1'-biphenyl]-4-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 3 [ka] A solution of 6-([1,1'-biphenyl]-4-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (1.20 g, 2.4 mmol) in water (40 mL) was added dropwise to a solution of NaBF4 (1.60 g, 14.5 mmol) in water (40 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (2 × 5 mL), then with MeOH (2 mL), and air-dried to obtain the title compound (1.14 g, 93%) as an orange powder;δ H(D2O / CD3OD,400MHz)7.50-7.67(3H,m),7.83-7.90(2H,m),7.95(2H,d,J=8.1Hz),8.13(2H,d,J=8.1Hz),8.68(1H,app.t,J=7.1Hz),8.79(1H,app. t,J=6.9Hz),9.21-9.29(2H,m),9.34(1H,s),9.58(1H,app.d,J=6.5Hz),9.69(1H,app.d,J=6.2Hz),9.86(1H,d,J=8.6Hz) and 9.92(1H,d,J=8.7Hz);δ F (D2O / CD3OD,376MHz)-150.38,-150.32;δ C (D2O / CD3OD, 100MHz) 125.51, 127.49, 127.81, 128.52, 130.09, 130.20, 130.63, 132.26, 132.35, 132.44, 138.04, 138.49, 139.53, 140.33, 141.06, 143.27, 146.90, 148.24 and 148.51.

[0101] 1-{2-oxo-2-[4-(trifluoromethyl)phenyl]ethyl}-[2,2'-bipyridine]-1-ium bromide [ka] A mixture of 2,2'-bipyridine (2 g, 12.8 mmol) and 2-bromo-1-(4-trifluoromethylphenyl)ethane-1-one (3.54 g, 13.3 mmol) was heated at 100°C for 45 minutes. The resulting solid was cooled and crystallized twice from EtOH / Et2O, followed by air drying to obtain the title compound (4.08 g, 75%) as a yellow powder. This was used in the next step without further purification.

[0102] 6-[4-(trifluoromethyl)phenyl]dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A mixture of 1-{2-oxo-2-[4-(trifluoromethyl)phenyl]ethyl}-[2,2'-bipyridine]-1-ium bromide (3.17 g, 7.5 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes and then cooled. The residue was filtered, washed with Et2O (3 × 50 mL), and crystallized from MeOH / diisopropyl ether. The residue was triturated with hot EtOH, cooled, filtered, and again triturated with isopropanol (5 mL), filtered, and air-dried to obtain the title compound (1.26 g, 35%) as a yellow powder;δ H (D2O,400MHz)7.90(2H,bd,J=8.1Hz),8.05(2H,bd,J=8.1Hz),8.51(1H,bt,J=6.6Hz),8.66(1H,bt,J=6.9Hz),9.07-9.1 5(2H,m),9.23(1H,s),9.34(1H,bd,J=6.5Hz),9.53(1H,bd,J=6.2Hz),9.72(1H,bd,J=8.6Hz) and 9.77(1H,bd,J=8.4Hz);δ F (D2O, 376MHz)-63.13;δ C (D2O, 100MHz) 123.46 (q,J=272Hz), 126.55, 126.57, 127.22, 127.37 (q,J=3.8Hz), 128.82 (q,J=1.4Hz), 130.89, 131.03, 131.36, 133.94 (q,J=32.9Hz), 135.22, 136.99, 137.86, 139.85, 142.09, 147.23, and 147.25.

[0103] 6-[4-(trifluoromethyl)phenyl]dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 4 [ka] A solution of 6-[4-(trifluoromethyl)phenyl]dipyrido[1,2-a:2’,1’-c]pyrazine-5,8-diium dibromide (1.20 g, 2.5 mmol) in water (40 mL) was added dropwise with stirring to a solution of NaBF4 (3.26 g, 29.6 mmol) in water (40 mL). Stirring was continued for 0.5 h, and the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried to give the title compound (0.96 g, 78%) as a purple powder; δ H (D2O / CD3OD, 400 MHz) 7.99 (2H, bd, J = 8.3 Hz), 8.07 (2H, bd, J = 8.3 Hz), 8.55 (1H, bt, J = 6.9 Hz), 8.69 (1H, bt, J = 6.8 Hz), 9.11 - 9.19 (2H, m), 9.27 - 9.33 (2H, m), 9.59 (1H, bd, J = 6.2 Hz), 9.79 (1H, bd, J = 8.6 Hz) and 9.84 (1H, bd, J = 8.4 Hz); δ F (D2O / CD3OD, 376 MHz) -151.65 (q, J = 1.1 Hz), -151.60 (bs), -62.85 (s). Due to low solubility, 13 the C spectrum could not be obtained.

[0104] 1-[2-(2,4-Dimethylphenyl)-2-oxoethyl]-[2,2’-bipyridine]-1-ium bromide [Chemical formula] A mixture of 2,2’-bipyridine (2 g, 12.8 mmol) and 2-bromo-1-(2,4-dimethylphenyl)ethan-1-one (3.44 g, 15.1 mmol) was heated at 100 °C for 45 min. The resulting solid was cooled, crystallized twice from EtOH / Et2O, collected by filtration, washed with Et2O (30 mL), and air-dried to give the title compound (4.24 g, 86%) as a pale yellowish brown powder; δ H(CD3OD, 400MHz) 2.42 (3H,s), 2.48 (3H,s), 6.35 (2H,m), 7.19-7.27 (2H,m), 7.57 (1H,ddd,J=1.0,4.8 and 7.7Hz), 7.73 (1H,d,J=8Hz), 8.06 (1H,app.d,J=8.1Hz), 8.13 (1H,dt,J=1.7 and 7.9Hz), 8.32 (1H,dt,J=1.4 and 6.4Hz), 8.38-8.41 (1H,m), 8.48 (1H,dd,J=1.0 and 8.0Hz), 8.86 (1H,dt,J=1.4 and 8.1Hz) and 9.12 (1H,dd,J=0.8 and 6.2Hz); δ C (CD3OD, 100MHz) 18.88, 18.93, 124.68, 125.19, 125.26, 125.73, 127.61, 128.56, 129.11, 131.63, 137.17, 138.83, 142.81, 145.54, 147.62, 148.34, 150.99 and 189.57.

[0105] 6-(2,4-dimethylphenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A mixture of 1-[2-(2,4-dimethylphenyl)-2-oxoethyl]-[2,2'-bipyridine]-1-ium bromide (3.11 g, 6.4 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes, cooled, decanted, and the residue was triturated with Et2O (3 × 50 mL) and precipitated twice from EtOH using diisopropyl ether. The resulting solid was crystallized from high-temperature MeOH / diisopropyl ether, filtered, washed with Et2O (2 × 30 mL), and vacuum-dried to obtain the title compound (2.65 g, 74%) as a yellow powder;δ H(D2O,400MHz)2.08(3H,s),2.39(3H,s),7.28-7.41(3H,m),8.48(1H,app.t,J=7.3Hz),8.63(1H,app.t,J=6. 9Hz),9.04-9.16(4H,m),9.49(1H,app.d,J=6.3Hz),9.70(1H,app.d,J=8.7Hz) and 9.75(1H,app.d,J=8.5Hz);δ C (D2O, 100MHz) 18.37, 20.65, 121.31, 126.35, 126.63, 127.22, 128.20, 130.84, 131.02, 131.15, 132.20, 136.19, 137.17, 138.00, 138.90, 139.42, 141.75, 144.27, 146.85 and 146.91.

[0106] 6-(2,4-dimethylphenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 5 [ka] A solution of 6-(2,4-dimethylphenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium bromide (2.60 g, 5.8 mmol) in water (40 mL) was added dropwise to a solution of NaBF4 (7.69 g, 69.9 mmol) in water (40 mL) with stirring. Stirring was continued for 0.5 hours, the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried to obtain the title compound (2.05 g, 76%) as a pale yellowish-brown powder;δ H (D2O / CD3OD,400MHz)2.14(3H,s),2.42(3H,s),7.32-7.46(3H,m),8.53(1H,app.t,J=6.9Hz),8.67(1H,app.t,J =7.0Hz),9.03-9.18(4H,m),9.55(1H,app.d,J=6.2Hz),9.75(1H,app.d,J=8.7Hz) and 9.81(1H,app.d,J=8.5Hz);δ C (D2O / CD3OD,376MHz)-150.97,-150.91;δ C(D2O / CD3OD, 100MHz) 19.56, 21.87, 122.98, 127.70, 128.09, 128.64, 129.74, 132.17, 132.50, 132.52, 133.74, 137.73, 138.87, 139.74, 140.37, 140.48, 143.23, 145.66, 148.19, and 148.31.

[0107] 1-(1-oxo-1-phenylpropan-2-yl)-[2,2'-bipyridine]-1-ium bromide [ka] A solution of 2,2'-bipyridine (8 g, 41.3 mmol) and 2-bromo-1-phenylpropan-1-one (8 g, 37.7 mmol) in MeCN (50 mL) was heated under reflux for 7 days. The resulting solution was cooled, the solvent was removed under reduced pressure, and the residue was washed with acetone. The resulting solid was crystallized from EtOH / Et2O and vacuum-dried to obtain the title compound (2.13 g, 15%) as a colorless powder;δ H (CDCl3,400MHz)2.15(3H,d,J=7.2Hz),6.92(1H,q,J=7.2Hz),7.33-7.38(1H,m),7.47-7.56(2H,m),7.66(1H,app.t,J=7.5Hz),7.81-8.89(2H,a δ C (CDCl3, 100MHz) 17.08, 65.60, 123.22, 124.71, 125.33, 126.32, 126.68, 127.70, 129.97, 131.92, 136.13, 142.72, 143.26, 146.03, 147.32, 150.52, and 190.35.

[0108] 6-Methyl-7-phenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A mixture of 1-(1-oxo-1-phenylpropan-2-yl)-[2,2'-bipyridine]-1-ium bromide (2.13 g, 5.8 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes. After cooling, the residue was filtered, washed with Et2O (3 × 50 mL), crystallized twice from EtOH / diisopropyl ether, filtered, and vacuum-dried to obtain the title compound (2.06 g, 82%) as a yellow powder. This was used in the next step without further purification.

[0109] 6-Methyl-7-phenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 6 [ka] A solution of 6-methyl-7-phenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium bromide (2.06 g, 4.8 mmol) in water (50 mL) was added dropwise to a solution of NaBF4 (6.29 g, 57.2 mmol) in water (50 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (2 × 10 mL), and air-dried to obtain the title compound (0.83 g, 39%) as a gray powder;δ H (CDCl3,400MHz)3.16(3H,s),7.56-7.64(2H,bm),7.76-7.87(3H,bm),8.43(1H,bt,J=8.1 Hz),7.74(1H,bt,J=7.5Hz),8.95-9.09(2H,m),9.16(1H,bt,J=8Hz) and 9.74-9.90(3H,m);δ F (CDCl3,376MHz)-150.78,-150.73;δ C (CDCl3, 100MHz) 19.10, 128.04, 128.39, 128.68, 131.47, 131.88, 132.35, 132.49, 134.18, 135.57, 135.78, 138.87, 138.94, 140.46, 140.95, 147.19, and 147.74.

[0110] 3-(bromoacetyl)thiophene [ka] A solution of Br2 (12 g, 75 mmol) in DCM (50 mL) was added dropwise to a solution of 3-acetylthiophene (9.45 g, 75 mmol) in DCM (50 mL) over 1 hour with stirring. The resulting solution was stirred at room temperature for 1 hour, washed with saturated NaHCO3 (2 × 100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was subjected to silica gel chromatography using DCM (30% in hexane) as the eluent. By removing the solvent under reduced pressure, the title compound (3.62 g, 23%) was obtained as a colorless powder;δ H (CDCl3, 400MHz) 4.34 (2H,s), 7.37 (1H,dd,J=2.8 and 5.1Hz), 7.58 (1H,dd,J=1.2 and 5.1Hz), and 8.18 (1H,dd,J=1.2 and 2.8Hz).

[0111] 1-[2-oxo-2-(thiophen-3-yl)ethyl]-[2,2'-bipyridine]-1-ium bromide [ka] A mixture of 2,2'-bipyridine (2 g, 12.8 mmol) and 3-(bromoacetyl)thiophene (2.73 g, 13.3 mmol) was heated at 100°C for 45 minutes. The resulting solid was cooled, triturated with high-temperature Et2O / EtOH, cooled, decanted, triturated with acetone (3 × 40 mL), filtered, and air-dried to obtain the title compound (3.02 g, 65%) as a yellow powder;δ H (D2O,400MHz)6.06(2H,bs),7.40-7.51(3H,m),7.79(1H,bd,J=7.9Hz),7.97(1H,bt,J=7.9Hz) ,8.15(1H,bt,J=7.2Hz),8.20-8.31(2H,m),8.69(1H,bt,J=7.9Hz) and 8.84(1H,bd,J=6.2Hz);δF (D2O,376MHz)-150.97,-150.91;δ C (D2O / CD3OD, 100MHz) 126.05, 126.35, 126.49, 127.64, 128.26, 129.98, 135.99, 136.89, 139.09, 147.43, 148.29, 148.58, 149.38, 152.06 and 186.43.

[0112] 6-(thiophen-3-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumdibromide [ka] A mixture of 1-[2-oxo-2-(thiophen-3-yl)ethyl]-[2,2'-bipyridine]-1-ium bromide (2.71 g, 7.5 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes. After cooling, the residue was filtered and washed with Et2O (3 × 50 mL). It was dissolved three times in hot methanol (20 mL), and the methanol solution was added to diisopropyl ether (40 mL) with stirring. The resulting precipitate was filtered and dissolved in hot EtOH (25 mL). Then, the solution was filtered to remove particles, and diisopropyl ether (30 mL) was added. The resulting precipitate was filtered, washed with diisopropyl ether, and vacuum dried to obtain the title compound (1.25 g, yield 39%) as a yellowish-brown powder. This was used in the next step without further purification;δ H (D2O,400MHz)7.42(1H,bd,J=5.0Hz),7.84(1H,bt,J=4.0Hz),8.14(1H,bs),8.52(1H,bt,J=7.1Hz),8.62(1H,bt ,J=7.0Hz),9.04-9.12(2H,m),9.18(1H,s),9.47-9.53(2H,m),9.67(1H,bd,J=8.7Hz) and 9.73(1H,bd,J=8.5Hz);δ C(D2O / CD3OD, 100MHz) 124.47, 125.88, 126.42, 127.03, 127.40, 130.31, 130.83, 130.89, 132.66, 133.03, 136.81, 137.79, 139.77, 141.67, 146.71, and 146.97.

[0113] 6-(thiophen-3-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium bistetrafluoroborate hexafluorophosphate Compound 7 [ka] A solution of 6-(thiophen-3-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (1.16 g, 2.7 mmol) in water (50 mL) was added dropwise to a solution of NaBF4 (10.83 g, 98.4 mmol) in water (50 mL) while stirring, filtering through a cotton stopper. Stirring was continued for 0.5 hours, the resulting precipitate was filtered and washed with water (2 × 5 mL). Ammonium hexafluorophosphate (3.95 g, 24.2 mmol) was added to the solution while stirring. The resulting precipitate was filtered, washed with water (2 × 5 mL), air-dried, then washed with MeOH (5 mL), and air-dried to obtain the title compound (1.40 g, 92%) as a gray powder;δ H (D2O,400MHz)7.43(1H,bd,J=4.6Hz),7.82-7.88(1H,bs),8.14(1H,bs),8.54(1H,bt,J=7.4Hz),8.63(1H,bt,J =7.1Hz),9.05-9.13(2H,m),9.18(1H,s),9.47-9.55(2H,m),9.68(1H,bd,J=8.8Hz)and9.74(1H,bd,J=8.3Hz) F (D2O,376MHz)-150.53,-150.48,-72.19(d,J=709.6Hz);δ P (D2O, 162MHz) -145.14 (sept J = 709.6). Due to its low solubility, 13 The C spectrum could not be obtained.

[0114] 1-[2-(2-fluorophenyl)-2-oxoethyl]-[2,2'-bipyridine]-1-ium bromide [ka] A mixture of 2,2'-bipyridine (2 g, 12.8 mmol) and 2-bromo-1-(2-fluorophenyl)ethane-1-one (2.88 g, 13.3 mmol) was heated at 100°C for 45 minutes. The resulting solid was triturated using high-temperature Et2O / EtOH. The solid product was recovered by filtration, washed with Et2O (2 × 50 mL), and air-dried to obtain the title compound (4.06 g, 85%) as a cream-colored powder;δ H (CD3OD, 400MHz) 6.22-6.27 (2H,m), 7.35 (1H,ddd,J=1.0, 8.3 and 11.9Hz), 7.43 (1H,dt,J=1.1 and 7.7Hz), 7.54 (1H,ddd,J=1.4, 4.8 and 7.5Hz), 7.74-7.80 (1H,m), 8.00 (1H,dt,J=1.9 and 7.5Hz), 8.04-8.14 (2H,m), 8.25-8.33 (2H,m), 8.48 (1H,dd,J=1.5 and 8.1Hz), 8.84 (1H,dt,J=1.5 and 7.9Hz) and 9.12 (1H,dd,J=1.5 and 6.2Hz); δ F (CD3OD,376MHz)-110.84--110.70(m);δ C (CD3OD,100MHz)116.57(d,J=23.2Hz),122.02(d,J=13.0Hz),125.06(d,J=3.2Hz),126.03,126.54,127.02,129.84,130.5 8(d,J=2.4Hz),136.41(d,J=9.4Hz),138.53,147.06,148.74,148.96,149.32,152.01,160.86,163.38 and 187.42(d,J=4Hz).

[0115] 6-(2-fluorophenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A mixture of 1-[2-(2-fluorophenyl)-2-oxoethyl]-[2,2'-bipyridine]-1-ium bromide (3.81 g, 10.2 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes, then cooled, the residue was filtered, and washed with Et2O (3 × 50 mL). The crude product was triturated with EtOH, then with hot EtOH / diisopropyl ether, filtered, washed with diisopropyl ether, and then triturated three times with hot EtOH (20 mL). The product was recovered by filtration, washed with Et2O (2 × 20 mL), and air-dried to obtain the title compound (2.34 g, 53%) as a dark gray powder;δ H (D2O,400MHz)7.42-7.59(2H,m),7.73(1H,bt,J=6.6Hz),7.81-7.88(1H,m),8.55(1H,bt,J=7.0Hz),8.67(1H,bt,J=6.9Hz),9. 08-9.18(2H,m),9.29(1H,s),9.35(1H,bd,J=6.6Hz),9.55(1H,bd,J=6.3Hz),9.73(1H,bd,J=8.6Hz) and 9.78(1H,bd,J=8.5Hz);δ F (D2O, 376MHz)-110.70;δ C (D2O,100MHz)112.98(d,J=14.6Hz),117.11(d,J=19.7Hz),126.41(d,J=3.5Hz),126 .48,127.21,127.60,131.01(d,J=6.0Hz),131.78,132.48(d,J=0.9Hz),136.15(d,J =8.7Hz), 137.23, 137.97, 139.81, 142.09, 147.25, 147.37, 159.14 and 161.64.

[0116] 6-(2-fluorophenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 8 [ka] A solution of 6-(2-fluorophenyl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (1.75 g, 4 mmol) in water (40 mL) was added dropwise to a solution of NaBF4 (6.62 g, 60.2 mmol) in water (40 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (3 × 5 mL), and air-dried to obtain the title compound (1.26 g, 70%) as a purple powder;δ H (D2O,400MHz)7.42-7.58(2H,m),7.69(1H,bt,J=7.5Hz),7.80-7.88(1H,m),8.53(1H,bt,J=7.2Hz),8.65(1H,bt,J=7.0Hz),9. 08-9.17(2H,m),9.27(1H,s),9.34(1H,bd,J=6.3Hz),9.53(1H,bd,J=6.3Hz),9.71(1H,bd,J=8.6Hz) and 9.76(1H,bd,J=8.5Hz);δ F (D2O, 376MHz) -150.53 (bq, J=1.4Hz), -150.48, -110.88. Due to low solubility, 13 The C spectrum could not be obtained.

[0117] 1-(2-oxo-1,2-diphenylethyl)-[2,2'-bipyridine]-1-ium bromide [ka] A solution of 2,2'-bipyridine (3.20 g, 20.5 mmol) and decyl bromide (4.00 g, 14.6 mmol) in MeCN (40 mL) was heated under reflux for 2 days, cooled, and the solvent was removed under reduced pressure. The residue was triturated with acetone / Et2O (1 / 1, 40 mL), filtered, and crystallized from EtOH / Et2O. The resulting precipitate was crystallized from EtOH (5 mL), filtered, and air-dried to obtain the title compound (0.96 g, 15%) as a yellow powder. This was used in the next step without further purification.

[0118] 6,7-Diphenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide [ka] A solution of 1-(2-oxo-1,2-diphenylethyl)-[2,2'-bipyridine]-1-ium bromide (0.96 g, 2.2 mmol) in PBr3 (10 mL) was heated under reflux for 15 minutes. After cooling, the product was filtered and triturated with hot EtOH (5 mL). The solid product was recovered by filtration, washed with EtOH (2 mL), and air-dried to obtain the title compound (0.63 g, 57%) as a pale green powder;δ H (D2O,400MHz)7.43-7.50(10H,m),8.43(2H,bt,J=7.2Hz),9.09(2H,bt,J=8.0Hz),9.15(2H,bd,J=6.6Hz) and 9.81(2H,bd,J=8.5Hz);δ C (D2O, 100MHz) 126.39, 126.90, 130.13, 130.59, 130.72, 131.98, 135.87, 137.54, 140.27 and 146.76.

[0119] 6,7-Diphenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(tetrafluoroborate) compound 9 [ka] A solution of 6,7-diphenyldipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (0.63 g, 1.3 mmol) in water (20 mL) was added dropwise to a solution of NaBF4 (2.80 g, 25.4 mmol) in water (20 mL) with stirring. Stirring was continued for 0.5 hours, and the resulting precipitate was collected by filtration, washed with water (2 × 2 mL), and air-dried to obtain the title compound (0.56 g, 86%) as a gray powder;δ H (D2O,400MHz)7.43-7.50(10H,m),8.42(2H,bt,J=7.1Hz),9.08(2H,bt,J=8.1Hz),9.15(2H,bd,J=6.6Hz) and 9.80(2H,bd,J=8.6Hz);δ F(D2O,376MHz)-150.56(q,J=1.35Hz),-150.50(bs);δ C (D2O, 100MHz) 126.36, 126.87, 130.13, 130.56, 130.70, 131.98, 135.86, 137.50, 140.28 and 146.77.

[0120] 2-(bromoacetyl)thiophene [ka] A solution of bromine (19.05 g, 6.1 ml, 119 mmol) in DCM (80 mL) was added dropwise to 2-acetylthiophene (15 g, 119 mmol) in DCM (80 mL) over 1 hour with stirring. The resulting solution was stirred for another 1 hour, washed with saturated NaHCO3 (2 × 200 mL) and saturated saline (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was distilled (100 °C, 4 mbar), and silica gel chromatography was performed using DCM (40% in hexane) as the eluent. By removing the solvent under reduced pressure, the title compound (9.92 g, 41%) was obtained as a pale yellow oil;δ H (CDCl3,400MHz) 4.36 (2H,s), 7.17 (1H,dd,J=3.9 and 4.9Hz), 7.72 (1H,dd,J=1 and 4.9Hz), and 7.81 (1H,dd,J=1 and 3.9Hz).

[0121] 1-[2-oxo-2-(thiophen-2-yl)ethyl]-[2,2'-bipyridine]-1-ium bromide [ka] A mixture of 2,2'-bipyridine (2 g, 12.8 mmol) and 2-(bromoacetyl)thiophene (2.73 g, 13.3 mmol) was heated at 100°C for 45 minutes. The resulting solid was cooled, stirred with Et2O / EtOH for 16 hours, filtered, and vacuum-dried to obtain the title compound (2.38 g, 51%) as a yellowish-brown powder. This was used in the next step without further purification.

[0122] 6-(thiophen-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumdibromide [ka] A mixture of 1-[2-oxo-2-(thiophen-2-yl)ethyl]-[2,2'-bipyridine]-1-ium bromide (2.38 g, 6.6 mmol) in PBr3 (15 mL) was heated under reflux for 15 minutes. After cooling, the residue was filtered, washed with Et2O (3 × 50 mL), and triturated with Et2O containing a few drops of EtOH. The resulting solid was triturated with warmed EtOH (160 mL), collected, and air-dried to obtain the title compound (1.48 g, 53%) as a dark green powder. This was used in the next step without further purification.

[0123] 6-(thiophen-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diiumbis(hexafluorophosphate) compound 10 [ka] A solution of 6-(thiophen-2-yl)dipyrido[1,2-a:2',1'-c]pyrazine-5,8-diium dibromide (1.42 g, 3.3 mmol) in water (100 mL) was added dropwise to a solution of NH4PF6 (5.46 g, 33.4 mmol) in water (100 mL) that was being stirred, while filtering through a cotton stopper. The resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried to obtain the title compound (1.34 g, 72%) as a yellowish-brown powder;δ H (D2O,400MHz)7.41(1H,bt,J=4.1Hz),7.73(1H,bd,J=3.4Hz),8.03(1H,bd,J=5.1Hz),8.56(1H,bt,J=7.1H z),8.65(1H,bt,J=7.1Hz),9.08-9.15(2H,m),9.30(1H,bs),9.51(1H,bd,J=6.3Hz) and 9.64-9.77(3H,m);δ F(D2O,376MHz)-72.15(d,J=710Hz);δ P (D2O, 162MHz) -145.11 (sept J=710Hz). Due to its low solubility, 13 The C spectrum could not be obtained.

[0124] 2-(pyridine-2-yl)-1H-benzimidazole [ka] A mixture of pyridine-2-carboxyaldehyde (6.00 g, 56 mmol) and o-phenylenediamine (6.06 g, 56 mmol) in EtOH (300 mL) was left in air for 2 days. The amount of solvent was reduced (approximately 50 mL), the precipitate was filtered, washed with MeOH (10 mL), and air-dried to obtain the title compound (2.26 g, 21%) as a yellow powder;δ H (CDCl3,400MHz) 7.27-7.34 (2H,m), 7.35-7.41 (1H,ddd,J=1.1,4.8 and 7.6Hz), 7.45-7.52 (1H,m), 7.82-7.91 (2H,m), 8.45 (1H,dt,J=1.1 and 7.9Hz), 8.64 (1H,ddd,J=1,1.7 and 5.8Hz) and 10.84 (1H,bs);δ C (CDCl3, 100MHz) 111.29, 120.14, 121.70, 122.73, 123.96, 124.64, 133.87, 137.38, 144.39, 148.30, 149.14 and 150.78.

[0125] 1-Methyl-2-(pyridine-2-yl)-1H-benzimidazole [ka] A mixture of 2-(pyridine-2-yl)-1H-benzimidazole (3.00 g, 15.4 mmol) and K2CO3 (3.18 g, 23 mmol) in dry DMF (30 mL) was stirred at room temperature. After 0.5 hours, MeI (2.62 g, 18.4 mmol) was added, and stirring was continued for 16 hours. The resulting mixture was poured into water (100 mL) and extracted with siRNA (3 × 300 mL). The combined extract was washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was filtered through silica gel using siRNA as the eluent, and the solvent was removed under reduced pressure to obtain the title compound (2.89 g, 90%) as a viscous orange oil;δ H (DMSO-d6, 400MHz) 4.22 (3H,s), 7.23-7.35 (2H,m), 7.51 (1H,ddd,J=1.2,4.9 and 7.5Hz), 7.61-7.66 (1H,m), 7.69-7.74 (1H,m), 7.99 (1H,dt,J=1.8,7.7Hz), 8.30 (1H,dt,J=1 and 7.9Hz) and 8.74 (1H,ddd,J=1,1.7 and 5.8Hz); δ C (DMSO-d6, 100MHz) 33.07, 111.24, 119.87, 122.80, 123.57, 124.67, 124.84, 137.58, 137.86, 142.50, 149.27, 150.18 and 150.57.

[0126] 1-Methyl-3-(2-oxo-2-phenylethyl)-2-(pyridine-2-yl)-1H-benzimidazole-3-ium bromide [ka] A mixture of 1-methyl-2-(pyridine-2-yl)-1H-benzimidazole (2.82 g, 13.5 mmol) and phenacyl bromide (2.68 g, 13.5 mmol) was heated at 100°C for 16 hours, allowed to cool, and then crystallized from EtOH at 0°C to obtain the title compound (4.12 g, 75%) as colorless columnar crystals; δ H(DMSO-d6,400MHz)4.18(3H,s),6.39(2H,s),7.57-7.63(2H,m),7.71-7.84(4H,m),8.00-8.06(2H,m),8.14-8.26(4H,m) and 8.70(1H,m);δ C (DMSO-d6, 100MHz) 34.22, 53.19, 114.34, 114.49, 127.72, 127.93, 127.98, 128.60, 128.92, 129.48, 132.12, 132.46, 134.10, 135.01, 138.78, 140.91, 147.97, 151.23 and 191.52.

[0127] 6-Phenylbenzimidazo[1,2-a]pyrido[2,1-c]pyrazine-5-iumtetrafluoroborate [ka] A mixture of 1-methyl-3-(2-oxo-2-phenylethyl)-2-(pyridine-2-yl)-1H-benzimidazole-3-ium (2.00 g, 4.9 mmol) in PBr3 (15 mL) was heated under reflux for 25 minutes, cooled, and diluted with Et2O (50 mL). The residue was filtered and washed with Et2O (3 × 50 mL). The residue was dissolved in MeOH (15 mL) and added dropwise with stirring to a solution of NaHCO3 (4.12 g, 4.9 mmol) in water (100 mL). Solid NaBF4 (10.78 g, 98 mmol) was added, and the resulting mixture was stirred for 0.5 hours and then filtered. The filter extract was dissolved in MeOH (100 mL) and poured into water (150 mL) to reduce the solvent. The resulting precipitate was filtered, triturated with MeOH (20 mL), then recovered by filtration and air-dried to obtain the title compound (0.84 g, 45%) as a dull green powder; δ H (DMSO-d6,400MHz)7.68-7.82(7H,m),8.15-8.27(2H,m),8.45-8.54(1H,m),8.80( 1H,t,J=8Hz), 8.96(1H,d,J=6.7Hz),9.39(1H,dd,J=1.4 and 8.3Hz) and 9.56(1H,s);δ C(DMSO-d6, 100MHz) 113.33, 121.09, 121.26, 124.67, 126.29, 127.21, 127.66, 127.74, 129.01, 130.22, 130.37, 131.77, 137.39, 137.64, 139.79, 143.65 and 144.09.

[0128] 13-Methyl-6-phenyl-13H-benzimidazo[1,2-a]pyrido[2,1-c]pyrazine-5,8-diiumbis(tetrafluoroborate) Compound 11 [ka] A mixture of 6-phenylbenzimidazo[1,2-a]pyrido[2,1-c]pyrazine-5-ium tetrafluoroborate (0.70 g, 1.86 mmol) in MeOTs (2.77 g, 14.9 mmol) was heated at 180°C for 1 hour, cooled, and diluted with Et2O (40 mL). The residue was filtered, triturated with Et2O (3 × 20 mL), and air-dried. The filterd material was dissolved in MeOH (20 mL) containing a few drops of water, and this was added dropwise with stirring to a solution of NaBF4 (4.09 g, 37.2 mmol) in water (100 mL). Stirring was continued for 0.5 hours, the resulting precipitate was filtered, washed with water (2 × 5 mL), and air-dried. The solid was triturated with MeOH (10 mL), filtered, and air-dried to obtain the title compound (0.69 g, 77%) as a khaki-colored powder; δ H (DMSO-d6,400MHz)4.89(3H,s),7.78-7.90(5H,m),8.09(1H,t,J=8Hz),8.18(1H,t,J=8Hz),8.57-8.64(2H, δ C(DMSO-d6, 100MHz) 36.72, 114.97, 115.04, 120.25, 126.54, 127.45, 127.87, 129.65, 130.67, 131.01, 131.51, 131.84, 131.91, 132.35, 132.66, 134.24, 135.63, 140.75 and 145.56.

[0129] 4-Phenyl-2-(pyridine-2-yl)quinoline [ka] A solution of 2-aminobenzophenone (6.51 g, 33 mmol) and 2-acetylpyridine (4.00 g, 33 mmol) in AcOH (80 mL) containing H2SO4 (2 mL) was heated under reflux for 24 hours. The mixture was cooled, poured into an ice / NH4OH solution, and extracted with CHCl3 (3 × 200 mL). The combined organic extract was washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was subjected to silica gel chromatography using an siRNA (0-100% in DCM) gradient as the eluent. The fluorescence band was collected, and the solvent was removed under reduced pressure. The residue was triturated with high-temperature siRNA / hexane, then cooled, recovered by filtration, washed with hexane, and air-dried to obtain the title compound (5.80 g, 62%) as yellow columnar crystals.

[0130] 4-Phenyl-2-(pyridine-2-yl)quinoline dibromide [ka] A solution of 4-phenyl-2-(pyridine-2-yl)quinoline (1.05 g, 3.7 mmol) in 1,2-dibromoethane (30 mL) was heated under reflux for 24 hours. After cooling, the precipitate was filtered, washed with hexane, and air-dried to obtain the title compound (1.43 g, 82%) as a dull yellow powder;δ H(CD3OD,400MHz)5.55(2H,bt,J=6.1Hz),5.81(2H,bt,J=6.1Hz),7.75-7.83(3H,m),7.86-7.94(2H,m),8.18(1H,bt,J= 8Hz), 8.45-8.56(3H,m),8.85(1H,bd,J=9.3Hz),8.96-9.05(2H,m),9.34(1H,bd,J=8.3Hz) and 9.45(1H,bd,J=5.7Hz);δ C (D2O, 100MHz) 29.69, 52.00, 118.74, 122.13, 129.01, 129.10, 129.19, 129.94, 130.11, 130.73, 131.27, 131.69, 134.67, 137.29, 139.77, 140.98, 141.63, 147.03, 147.75, and 161.30.

[0131] 4-Phenyl-2-(pyridine-2-yl)quinoline bis(tetrafluoroborate) compound 12 [ka] A solution of 4-phenyl-2-(pyridine-2-yl)quinoline dibromide (1.43 g, 3 mmol) in MeOH (20 mL) was added dropwise to a solution of NaBF4 (4 g, 36.6 mmol) in water (100 mL) with stirring. Stirring was continued for 0.5 hours, then an additional NaBF4 (13.39 g, 122 mmol) was added, and stirring was continued for another 0.5 hours. An additional NaBF4 (13.29 g, 122 mmol) was added again, and stirring was continued for another 0.5 hours to induce precipitation. The resulting precipitate was filtered, washed with water (2 × 20 mL), and air-dried to obtain the title compound (1.47 g, 100%) as a yellow-green powder;δ H (DMSO-d6,400MHz)4.68(2H,bs),4.93(2H,bs),6.94-7.11(5H,m),7.39(1H,bt,J=7.6Hz),7.64-7.74(3H,m) ,7.97(1H,bd,J=8.7Hz),8.12(1H,s),8.20(1H,bt,J=7.5Hz),8.39(1H,bd,J=8Hz) and 8.56(1H,bd,J=5.6Hz);δ F(DMSO-d6,376MHz)-153.53,-153.48;δ C (DMSO-d6, 100MHz) 45.53, 51.18, 117.67, 120.99, 128.24, 128.42, 128.54, 129.02, 129.33, 130.21, 130.70, 131.12, 133.70, 136.96, 138.97, 139.86, 140.31, 146.19, 147.38 and 160.95.

[0132] 2-amino-4'-methoxybenzophenone [ka] A solution of 4-bromoanisole (30.00 g, 160.4 mmol) in THF (100 mL) was added to Mg (4.29 g, 176.5 mmol) pretreated with I2, and the mixture was heated at 70°C for 1 hour. The resulting 4-MeOC6H4MgBr solution was cooled, solid 2-aminobenzonitrile (6.31 g, 53.5 mmol) was added, and the mixture was stirred at room temperature for 16 hours. A solution of concentrated HCl (40 mL) and water (50 mL) was carefully added. The resulting mixture was heated under reflux for 1 hour, then cooled, neutralized with NaOH (2 M), and extracted with DCM (4 × 50 mL). The combined extracts were washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. Silica gel chromatography was performed on the residue using DCM as the eluent, and a yellow band was recovered. By removing the solvent under reduced pressure, the title compound (11.16 g, 92%) was obtained as a viscous yellow oil.

[0133] 4-(4-methoxyphenyl)-2-(pyridine-2-yl)quinoline [ka] A solution of 2-amino-4'-methoxybenzophenone (5.00 g, 22 mmol) and 2-acetylpyridine (2.66 g, 22 mmol) in AcOH (80 mL) containing H2SO4 (2 mL) was heated under reflux for 16 hours. The resulting solution was poured into ice / NH4OH (100 mL) and extracted with DCM (3 × 80 mL). The combined extract was washed with water (100 mL), dried, and the solvent was removed under reduced pressure using (Na2SO4). Using DCM as the eluent, the residue was filtered through neutral alumina. The solvent was removed under reduced pressure, the residue was triturated with ELISA (5 mL), and air-dried to obtain the title compound (3.59 g, 52%) as a pale yellowish-brown powder.

[0134] 14-(4-methoxyphenyl)-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium dibromide [ka] A solution of 4-(4-methoxyphenyl)-2-(pyridine-2-yl)quinoline (1.00 g, 3.2 mmol) in 1,2-dibromoethane (15 mL) was heated under reflux for 16 hours. After cooling, the residue was filtered, washed with Et2O (2 × 30 mL), and air-dried to obtain the title compound (0.90 g, 56%) as an orange powder.

[0135] 14-(4-methoxyphenyl)-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diiumbis(tetrafluoroborate) and bis(hexafluorophosphate) compounds 13 and 14 [ka] A solution of 14-(4-methoxyphenyl)-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium dibromide (0.90 g, 1.8 mmol) in water (20 mL) was added dropwise to a solution of NaBF4 (3.96 g, 36 mmol) in water (100 mL) with stirring. Stirring was continued for 0.5 hours, after which MeOH (10 mL) was added and the solution was heated to dissolve. Solid NaBF4 (39.6 g, 180 mmol) was added to the solution and the mixture was stirred for 0.5 hours. The precipitate was collected by filtration, washed with water (2 × 5 mL), and air-dried to obtain 14-(4-methoxyphenyl)-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium bis(tetrafluoroborate) (0.56 g, 61%) as an orange powder; 1 1H NMR (400MHz, CD3OD / D2O)δ H 3.99(3H,s),5.40-5.47(2H,m),5.62-5.70(2H,m),7.34(2H,d,J=8.8Hz),7.88(2H,d,J=8.8Hz),8.14(1H,br.t,J=7.7Hz),8.39-8.50(2H, m),8.54(1H,bd,J=8Hz),8.68(1H,br.d,J=9Hz),8.83(1H,s),8.98(1H,br.t,J=7.8Hz),9.14(1H,br.d,J=8Hz) and 9.32(1H,br.d,J=5.7Hz); 19 F NMR (376 MHz, CD3OD / D2O) δ F -151.65 (bs), -151.60 (bs); 13 ¹³C NMR (100 MHz, CD3OD / D2O)δ C46.06, 52.12, 55.55, 115.11, 118.23, 121.24, 126.98, 128.73, 129.61, 129.65, 130.98, 131.71, 132.62, 137.68, 139.85, 140.43, 140.81, 146.91, 148.25, 161.44 and 162.59. Combine the water used for washing and solid NH4PF6(5 (0.87 g, 36 mmol) was added; the resulting precipitate was collected by filtration, washed with water (2 × 5 mL) and MeOH (2 mL), and air-dried to obtain 14-(4-methoxyphenyl)-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium bis(hexafluorophosphate) (0.33 g, 20%) as an orange powder; 1 1H NMR (400MHz, CD3OD / D2O)δ H 4.01 (3H,s), 5.43-5.50 (2H,m), 5.65-5.72 (2H,m), 7.36 (2H,d,J=8.8Hz), 7.90 (2H,d,J=8.8Hz), 8.17 (1H,dd,J=6.7 and 8.9Hz), 8.44-8.51 (2H,m), 8.56 (1H,dd,J=1.5 and 8.6Hz), 8.71 (1H,d,J=8.8Hz), 8.86 (1H,s), 9.00 (1H,app.dt,J=1.5 and 8.1Hz), 9.17 (1H,dd,J=1.3 and 8.3Hz), and 9.34 (1H,dd,J=1.3 and 6.0Hz); 19 F NMR (376 MHz, CD3OD / D2O) δ F -70.15 (d, J = 710 Hz); Due to the low solubility of this substance, 13 The 13C NMR spectrum could not be recorded.

[0136] 2-amino-4'-(trifluoromethyl)benzophenone [ka] A solution of 4-bromotrifluorobenzene (15.0 g, 66.7 mmol) in THF (70 mL) was added to Mg (1.6 g, 70 mmol) pretreated with I2, and the mixture was heated at 70°C for 1 hour. Solid 2-aminobenzonitrile (2.62 g, 22.2 mmol) was added to the solution of 4-F3CC6H4MgBr, and the mixture was stirred at room temperature for 16 hours. A mixture of concentrated HCl (10 mL) and water (50 mL) was carefully added. The resulting mixture was heated under reflux for 1 hour, then cooled and neutralized (NaOH, 2 M). The mixture was extracted with SiO2 (3 × 50 mL), the combined extract was washed with water (100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was triturated with hexane to obtain the title compound (4.41 g, 75%) as an orange powder.

[0137] 2-(pyridine-2-yl)-4-[4-(trifluoromethyl)phenyl]quinoline [ka] A solution of 2-amino-4'-(trifluoromethyl)benzophenone (4.41 g, 16.6 mmol) and 2-acetylpyridine (2.01 g, 16.6 mmol) in AcOH (60 mL) containing H2SO4 (1.5 mL) was heated under reflux for 16 hours. The resulting solution was poured into ice / NH4OH (100 mL) and extracted with DCM (4 × 50 mL). The combined extract was washed with water (2 × 100 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was chromatographed using neutral alumina with DCM (35% in petroleum ether (boiling point 40-60°C)) as the eluent. A band with an Rf of approximately 0.4 was recovered, and the solvent was removed under reduced pressure. The residue was crystallized from high-temperature petroleum ether (boiling point 40-60°C), filtered, washed with petroleum ether (boiling point 40-60°C), and air-dried to obtain the title compound (2.05 g, 35%) as a pale yellow powder.

[0138] 14-[4-(trifluoromethyl)phenyl]-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium dibromide [ka] A solution of 2-(pyridine-2-yl)-4-[4-(trifluoromethyl)phenyl]quinoline (1.00 g, 2.8 mmol) in 1,2-dibromoethane (15 mL) was heated under reflux for 16 hours. After cooling, the residue was filtered, washed with Et2O (2 × 30 mL), and air-dried to obtain the title compound (0.44 g, 29%) as an orange powder.

[0139] 14-[4-(trifluoromethyl)phenyl]-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diiumbis(hexafluorophosphate) Compound 15 [ka] A solution of 14-[4-(trifluoromethyl)phenyl]-6,7-dihydropyrido[2',1':3,4]pyrazino[1,2-a]quinoline-5,8-diium dibromide (0.44 g, 0.8 mmol) in water (20 mL) was added dropwise to a solution of NH4PF6 (1.33 g, 8 mmol) in water (20 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (2 × 5 mL), and air-dried to obtain the title compound (0.45 g, 83%) as a pale lime-colored powder. 1 1H NMR (400MHz, CD3OD / D2O)δ H 5.47-5.55(2H,m),5.75-5.82(2H,m),8.05(2H,d,J=8.2Hz),8.11(2H,d,J=8.2Hz),8.22(1H,br.t,J=7.3Hz),8.38(1H,br.d, J=8.3Hz), 8.48-8.57(2H,m),8.83(1H,br.d,J=91Hz),8.97-9.06(2H,m),9.23(1H,br.d,J=8Hz) and 9.40(1H,br.d,J=5.9Hz); 19 F NMR (376 MHz, CD3OD / D2O) δ F -73.82 (d, J=710Hz), -63.95 (s); Due to the low solubility of this substance, 13 The 13C NMR spectrum could not be recorded.

[0140] 4,4'-(pyrazine-2,5-diyl)bis(1-hexylpyridine-1-ium)bis(tetrafluoroborate) Compound 16 [ka] A solution of 4,4'-(pyrazine-2,5-diyl)bis(1-hexylpyridine-1-ium)diozide (1.90 g, 2.9 mmol) in MeOH (20 mL) was added dropwise to NaBF4 (3.81 g, 34.6 mmol) in water (120 mL) with high-speed stirring. The resulting precipitate was filtered, dissolved in warmed MeOH (50 mL), and added dropwise to NaBF4 (7.62 g, 69.2 mmol) in water (300 mL) with high-speed stirring. The resulting precipitate was filtered, washed with water (2 × 10 mL), and air-dried to obtain the title compound (1.23 g, 74%) as a pale yellowish-brown powder. The volume of the filtrate was reduced (approximately 80 mL), the residue was filtered, washed with water (5 mL), and then dissolved in warmed MeOH (10 mL). This solution was added dropwise to NaBF4 (7.62 g, 69.2 mmol) in water (100 mL) with vigorous stirring, the residue was filtered, washed with water (2 × 5 mL), and air-dried to obtain 0.37 g (22%) of the second product as a pale yellow powder;δ H (CD3OD,400MHz)0.95(6H,t,J=7Hz),1.33-1.53(12H,m),2.06-2.17(4H,m),4.7 3(4H,t,J=7.6Hz),8.95(4H,d,J=6.7Hz),9.18(4H,d,J=6.7Hz) and 9.78(2H,s);δ F (CD3OD,376MHz)-154.31,-154.26;δ C (CD3OD, 100MHz) 12.85, 22.07, 25.49, 30.90, 31.05, 61.57, 125.26, 143.85, 145.26, 147.66 and 150.75.

[0141] 4,4'-(pyrazine-2,5-diyl)bis[1-(2,4-dinitrophenyl)pyridine-1-ium]dichloride [ka] A solution of 2,5-di(pyridine-4-yl)pyrazine (1.71 g, 7.3 mmol) and 1-chloro-2,4-dinitrobenzene (8.88 g, 43.8 mmol) in EtOH (30 mL) was refluxed for 16 hours, cooled, filtered, washed with EtOH (10 mL), and air-dried to obtain the title compound (1.79 g, 38%) as a yellow powder. The volume of the solution was reduced (approximately 20 mL), heated under reflux for 16 hours, and then cooled to approximately 40°C. The residue was filtered, washed with EtOH (5 mL), and air-dried to obtain the second product (1.78 g, 38%) as a yellow powder;δ H (CD3OD,400MHz)8.42(2H,d,J=8.6Hz),8.99(2H,t,J=8.6Hz),9.30(4H,d,J=6.1Hz),9.35(2H,bs),9.54(4H,bd,J=6.1Hz) and 10.02(2H,s);δ C (CD3OD, 100MHz) 121.87, 125.24, 129.82, 131.23, 138.59, 143.26, 144.69, 146.67, 147.70, 149.93 and 153.44.

[0142] 4,4'-(pyrazine-2,5-diyl)bis[1-(p-tolyl)pyridine-1-ium]dichloride [ka] A solution of 4,4'-(pyrazine-2,5-diyl)bis[1-(2,4-dinitrophenyl)pyridine-1-ium]dichloride (0.70 g, 1.1 mmol) and p-toluidine (0.70 g, 6.5 mmol) in water (50 mL) was refluxed for 16 hours. The mixture was cooled, then filtered, and the aqueous filtrate was washed with CHCl3 (3 × 50 mL). The CHCl3 extract was discarded, and water was removed under reduced pressure. The residue was triturated with acetone, filtered, and air-dried to obtain the title compound (0.40 g, 75%) as a green powder;δ H (CD3OD,400MHz)2.56(6H,s),7.63(4H,d,J=7.8Hz),8.83(4H,d,J=7.8Hz),9.14(4H,d,J =6.2Hz),9.45(4H,d,J=6.2Hz) and 9.94(2H,s);δ C (CD3OD, 100MHz) 19.80, 123.77, 125.26, 130.88, 140.46, 142.71, 144.26, 145.18, 147.68 and 151.17.

[0143] 4,4'-(pyrazine-2,5-diyl)bis[1-(p-tolyl)pyridine-1-ium]bis(tetrafluoroborate) Compound 17 [ka] A solution of 4,4'-(pyrazine-2,5-diyl)bis[1-(p-tolyl)pyridine-1-ium]dichloride (0.40 g, 0.8 mmol) in hot water (30 mL) was added dropwise to a solution of NaBF4 (1.08 g, 9.8 mmol) in water (20 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (2 × 3 mL), and air-dried to obtain the title compound (0.37 g, 77%) as a yellowish-brown powder;δ H [(CD3)2CO,400MHz] 2.53(6H,s),7.64(4H,d,J=8.2Hz),7.94(4H,d,J=8.2Hz),9.24(4H,bs),9.58(4H,bs) and 10.04(2H,s);δ F [(CD3)2CO, 376MHz] -151.50 and -151.45; δC [(CD3)2CO, 100MHz] 20.24, 124.33, 125.73, 131.01, 140.67, 142.54, 144.64, 145.59, 147.82, and 151.16.

[0144] 3,6-di(pyridine-4-yl)-1,2,4-triazine [ka] Pyridine-4-carboxyaldehyde (2.36 g, 22 mmol) was added to a suspension of (1Z,2Z)-2-hydrazinylidene-2-(pyridine-4-yl)acetaldehyde oxime (3.62 g, 22 mmol) in AcOH (25 mL). The resulting mixture was stirred at room temperature for 1 hour, heated under reflux for 0.5 hours, then cooled and diluted with water (60 mL). The residue was filtered, washed with water (3 × 10 mL), and air-dried. The residue was triturated with hot EtOH (30 mL), cooled, filtered, and air-dried to obtain the title compound (3.64 g, 70%) as a yellow powder;δ H (DMSO-d6, 400MHz) 8.27 (2H,dd,J=1.6 and 4.5Hz), 8.39 (2H,dd,J=1.6 and 4.5Hz), 8.86-8.91 (4H,m) and 9.71 (1H,s); δ C (DMSO-d6, 100MHz) 121.40, 121.93, 140.58, 142.00, 149.25, 151.25, 151.41, 154.77 and 161.53.

[0145] 4,4'-(1,2,4-triazine-3,6-diyl)bis(1-hexylpyridine-1-ium)diozide [ka] A solution of 3,6-di(pyridine-4-yl)-1,2,4-triazine (1.50 g, 6.4 mmol) and 1-iodohexane (8.12 g, 38.3 mmol) in MeCN (30 ml) was heated under reflux for 16 hours, cooled, and the solvent was removed under reduced pressure. The residue was triturated with Et2O (3 × 50 mL) and vacuum-dried to obtain the title compound (4.08 g, 97%) as a brown powder;δ H (DMSO-d6,400MHz)0.79-0.92(6H,m),1.18-1.39(12H,m),1.92-2.07(4H,m),4.68-4.81(4H,m),9.05 (2H,d,J=6.9Hz),9.09(2H,d,J=6.8Hz),9.36(2H,d,J=6.9Hz),9.41(2H,d,J=6.9Hz) and 10.04(1H,s);δ C (d6-DMSO, 100MHz) 14.33, 22.35, 22.36, 25.56, 29.98, 30.55, 31.06, 31.15, 31.22, 33.30, 61.40, 61.47, 125.92, 126.51, 146.31, 146.65, 147.80, 148.85, 150.95, 153.14 and 159.90.

[0146] 4,4'-(1,2,4-triazine-3,6-diyl)bis(1-hexylpyridine-1-ium)bis(hexafluorophosphate) Compound 18 [ka] A solution of 4,4'-(1,2,4-triazine-3,6-diyl)bis(1-hexylpyridine-1-ium)diozide (4.08 g, 6.2 mmol) in MeOH (30 mL) was added dropwise to a solution of NH4PF6 (6.05 g, 37.1 mmol) in water (100 mL) with stirring. Stirring was continued for 0.5 hours, the precipitate was filtered, washed with water (3 × 10 mL), and air-dried to obtain the title compound (3.01 g, 68%) as a yellow powder;δ H(CD3OD,400MHz)0.88-0.97(6H,m),1.31-1.60(12H,m),2.21-2.33(4H,m),4.99-5.07( 4H,m),9.20(2H,d,J=6.6Hz),9.32(2H,d,J=6.5Hz),9.47-9.53(4H,m) and 10.05(1H,s);δ F (CD3OD,376MHz)-72.46(d,J=710Hz);δ C (CD3OD, 100MHz) 13.29, 22.15, 25.55, 30.97, 31.24, 31.28, 62.23, 62.29, 126.00, 126.61, 145.99, 146.19, 148.45, 149.54, 149.86, 153.16 and 159.90.

[0147] 2,3-Diphenylthieno[3,4-b]pyrazine [ka] 2,5-Dibromo-3,4-Dinitrothiophene (6.00 g, 18.1 mmol) was suspended in HCl aqueous solution (12 M, 110 mL) and stirred at 0°C. Then, while maintaining a temperature below 20°C, tin powder (15.10 g, 127.3 mmol) was added in small amounts. The reaction mixture was stirred until all the tin was consumed. The reaction mixture was then allowed to stand at -20°C for 16 hours, at which point a colorless precipitate formed. The precipitate was collected by vacuum filtration and then washed with ether (2 × 20 mL). The resulting colorless solid was then dissolved in EtOH (100 mL) containing benzyl (3.80 g, 18.1 mmol) and trimethylamine (5 mL). The solution was refluxed for 4 hours. The reaction mixture was then cooled to room temperature, and water (200 mL) was added. Subsequently, the reaction mixture was extracted with DCM (3 × 100 mL), the organic phase was combined, dried (Na₂SO₄), filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel chromatography [SiO₂:hexane = 1:9] to obtain the title compound as a pale yellowish-brown solid. Yield 3.00 g, 57%. δ H[CDCl3,400MHz] 8.05 (2H,s), 7.50-7.38 (4H,m) and 7.38-7.22 (6H,m); δ C [CDCl3, 100MHz] 153.5, 141.8, 139.3, 129.8, 129.0, 128.3, and 117.7.

[0148] 5,7-Dibromo-2,3-Diphenylthieno[3,4-b]pyrazine [ka] To a solution containing 2,3-diphenylthieno[3,4-b]pyrazine (3.00 g, 10.4 mmol) in a mixture of CHCl3 and trifluoroacetic acid (1:1 v / v, 64 mL), N-bromosuccinimide (4.00 g, 22.5 mmol) was added. The reaction mixture was then stirred at room temperature for 16 hours. Water (100 mL) was added to the reaction mixture, and then extracted with SiO2 (3 × 100 mL). The organic layers were combined, dried (Na2SO4), filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel chromatography [eluent = DCM:hexane gradient from 3:7 to 1:1] to obtain the title compound as a green solid. Yield 1.20 g, yield 26%. δ H [CDCl3,300MHz] 7.51-7.42 (4H,m) and 7.41-7.27 (6H,m);δ C [CDCl3, 75MHz] 154.8, 139.4, 138.4, 130.0, 129.5, 128.3 and 1051.

[0149] 2,3-diphenyl-5,7-di(pyridine-4-yl)thieno[3,4-b]pyrazine [ka] 5,7-Dibromo-2,3-Diphenylthieno[3,4-b]pyrazine (1.20 g, 2.7 mmol) and 4-Pyridineboronic acid pinacol ester (1.40 g, 6.8 mmol) were dissolved in a mixture of DME and H2O (2:1, 111 mL). The solution was then degassed with N2 for 30 minutes, after which Na2CO3 (0.86 g, 8.1 mmol) and Pd(PPh3)4 (0.32 g, 0.27 mmol) were added. The reaction mixture was then heated and stirred in N2 at 90°C for 5 days. The reaction mixture was cooled to room temperature, and water (100 mL) was added. The reaction mixture was extracted with ELISA (3 × 100 mL), followed by dichloromethane (2 × 200 mL). The organic phases were combined and dried (Na2SO4), filtered, and the solvent was removed under reduced pressure. The resulting residue was subjected to silica gel chromatography [eluent = 1:19 MeOH:SiO] to obtain the compound indicated in the title as a red solid. δ H [CDCl3,400MHz] 8.72(4H,dd,J=4.6,1.5Hz),8.23(4H,dd,J=4.6,1.5Hz),7.62-7.51(4H,m) and 7.48-7.33(6H,m);δ C [CDCl3, 100MHz] 154.1, 150.6, 140.9, 139.9, 138.8, 130.3, 130.0, 129.6, 128.4, and 121.6.

[0150] 4,4'-(2,3-diphenylthieno[3,4-b]pyrazine-5,7-diyl)bis(1-benzylpyridine-1-ium)bis(tetrafluoroborate) Compound 19 [ka] A mixture of 2,3-diphenyl-5,7-di(pyridine-4-yl)thieno[3,4-b]pyrazine (0.2 g, 0.45 mmol), benzyl bromide (0.77 g, 0.54 mL, 4.52 mmol), and MeCN (10 mL) was heated at 80°C for 16 hours. After cooling to room temperature, the reaction mixture was filtered, and the resulting orange precipitate was washed with MeCN (2 × 5 mL). The orange solid was dissolved in hot MeOH (25 mL) and dropped through a cotton stopper into a stirred solution of NaBF4 (10 g) in H2O (200 mL), forming an orange precipitate. The resulting precipitate was collected by vacuum filtration, washed with water (50 mL), and then dried under reduced pressure to obtain the title compound as an orange powder. Yield 0.31 g, yield 86%. δ H [(CD3)2SO,400MHz] 9.32(4H,br.app.s),9.08(4H,br.app.s),7.93-7.15(20H,br.m) and 5.90(4H,br.s);δ C * [(CD3)2SO, 100MHz] 175.2, 155.8, 146.1, 145.1, 1426, 137.9, 134.3, 130.0 (br.s), 129.5, 129.3, 129.0, 128.4, 124.9 and 62.9; δ F [(CD3)2SO,376MHz] -148.19(br.app.s). * Due to the broad and simultaneous existence of resonance, all 13 C{ 1 The H signal was not observed.

[0151] 2,5-di(pyridine-4-yl)pyrazine [ka] A mixture of 2,5-dibromopyrazine (2.25 g, 9.5 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (5.81 g, 28.3 mmol), K2CO3 (3.91 g, 28.3 mmol), and Pd(PPh3)4 (0.55 g, 5 mol%) in degassed PhMe and EtOH (80 ml, 1:1) was heated under reflux in N2 for 48 hours. The cooled solution was filtered through Celite, and the solvent was removed under reduced pressure. The residue was subjected to chromatography on silica using a gradient from MeOH (10% in siRNA) to MeOH (20% in DCM) as the eluent. The band with Rf = 0.5 (5% MeOH in DCM) was recovered, and the solvent was removed under reduced pressure. The residue was triturated with high-temperature siRNA (30 mL), cooled, filtered, then washed with siRNA (20 mL) and hexane (20 mL), and air-dried to obtain the title compound (1.32 g, 60%) as a pale salmon pink powder; δ H (CDCl3,400MHz) 8.01 (4H,dd,J=1.4 and 4.6Hz), 8.84 (4H,dd,J=1.4 and 4.6) and 9.23 (2H,s); δ C (CDCl3, 100MHz) 120.83, 141.80, 142.92, 149.76 and 150.87.

[0152] 4,4'-(pyrazine-2,5-diyl)bis(1-hexylpyridine-1-ium)diozide [ka] A mixture of 2,5-di(pyridine-4-yl)pyrazine (0.70 g, 3 mmol) and 1-iodohexane (3.80 g, 17.9 mmol) in MeCN (40 mL) was heated under reflux in N2 for 24 hours, then cooled and diluted with Et2O (40 mL). The residue was filtered, washed with Et2O (3 × 30 mL), and air-dried to obtain the title compound (1.90 g, 96%) as a red powder;δ H(CD3OD,400MHz)0.96(6H,t,J=7Hz),1.34-1.54(12H,m),2.06-2.17(4H,m),4. 74(4H,t,J=7.6Hz),8.98(4H,d,J=6.7Hz),9.23(4H,d,J=6.7) and 9.81(2H,s);δ C (CD3OD, 100MHz) 12.85, 22.08, 25.52, 30.91, 31.08, 61.58, 125.29, 143.92, 145.32, 147.65 and 150.74.

[0153] 1,4-Dihydroquinoxaline-2,3-dione [ka] To a mixture of oxalic acid (14.60 g, 162.4 mmol) in water (150 mL) and HCl (12 M) (30 mL), heated to 100 °C, o-phenylenediamine (15.00 g, 138.8 mmol) was added. The reaction mixture was then heated at 100 °C for 1 hour. Afterward, the reaction mixture was cooled to room temperature, and crushed ice (70 g) was added. The resulting colorless needle-shaped crystals were collected by filtration, washed with water (3 × 50 mL), and dried under reduced pressure to obtain the title compound as colorless needle-shaped crystals. Yield: 15.23 g, yield: 68%. δ H [(CD3)2SO,300MHz] 11.96(2H,br.s) and 7.22-7.01(4H,m);δ C [(CD3)2SO, 75MHz] 155.2, 125.6, 123.01 and 115.2.

[0154] 1H,1'H-2,2'-bibenzo[d]imidazole [ka] 1,4-Dihydroquinoxaline-2,3-dione (8.00 g, 50 mmol) was added to diethylene glycol (50 mL), and the mixture was heated to 250°C. Then, o-phenylenediamine (5.84 g, 138.8 mmol) was added, and the reaction mixture was heated at 250°C for 2.5 hours. The reaction mixture was cooled to 50°C, and water (30 mL) was added. The reaction mixture was stirred for 20 minutes, and the resulting yellow precipitate was collected by filtration. The yellow solid was washed with water (3 × 30 mL), followed by methanol (200 mL), and dried under reduced pressure. The solid was then recrystallized from high-temperature acetic acid, and subsequently washed with high-temperature ethyl acetate / MeOH to obtain the title compound as a yellow solid. Yield: 3.66 g, 32%. δ H [(CD3)2SO,300MHz] 13.58(br.2H,s),7.69(4H,br.app.s) and 7.44-7.17(4H,m);δ C [(CD3)2SO, 75MHz] 155.2, 143.8, 125.6, 123.1 and 115.2.

[0155] 5,6,7,12,13,14-Hexahydro-4b,7a,11b,14a-Tetraazadiindeno[1,2,3-ef:1',2',3'-kl]heptalene-7a,14a-Diium diiodide [ka] 1H,1'H-2,2'-bibenzo[d]imidazole (1.50 g, 6.4 mmol) and NaOH (0.67 g, 16.7 mmol) were suspended in DMF (25 mL), and the mixture was heated to 40°C. Then, 1,3-diiodopropane (10.93 g, 4.24 mL, 36.9 mmol) was added, and the reaction mixture was heated at 40°C for 0.5 hours. The reaction mixture was cooled to room temperature, and the resulting dark red / brown precipitate was collected by filtration. The compound was then triturated with acetone (3 × 20 mL) and dried under reduced pressure to obtain the title compound as a dark red / brown solid. Yield: 1.46 g, yield 40%. δ H[(CD3)2SO,300MHz] 8.44(4H,dd,J=6.4,3.1Hz),8.01(4H,dd,J=6.4,3.1Hz),5.09(8H,t,J=6.1Hz) and 2.99(4H,quin,J=6.0Hz);δ C [(CD3)2SO, 75MHz] 135.3, 132.5, 129.2, 114.4, 46.1 and 27.1.

[0156] 5,6,7,12,13,14-Hexahydro-4b,7a,11b,14a-Tetraazadiindeno[1,2,3-ef:1',2',3'-kl]heptalene-7a,14a-Diium bis(tetrafluoroborate) Compound 20 [ka] 5,6,7,12,13,14-Hexahydro-4b,7a,11b,14a-tetraazadiindeno[1,2,3ef:1',2',3-kl]heptalene-7a,14a-diium diiodide (0.5 g, 0.88 mmol) was dissolved in hot MeOH (35 mL) and added dropwise through a cotton stopper to a stirred solution of NaBF4 (15.0 g) in H2O (300 mL), forming a yellow precipitate. The precipitate was collected by vacuum filtration, washed with water (20 mL), and then dried under reduced pressure to obtain the title compound as a yellow powder. Yield: 0.43 g, yield: 86%.δ H [(CD3)2SO,300MHz] 8.42(4H,dd,J=6.3,3.0Hz),8.02(4H,dd,J=6.3,3.0Hz),5.05(8H,t,J=6.2Hz) and 2.95(4H,quin,J=6.0Hz);δ C [(CD3)2SO, 75MHz] 135.2, 132.5, 129.2, 114.3, 45.9 and 27.2; δ F [(CD3)2SO,376MHz] -148.27(8F,br.m).

[0157] 10-Phenyl-2,3-dihydro-1H-pyrido[2',1':3,4][1,4]diazepino[1,2-a]quinoline-4,15-diiumbis(hexafluorophosphate) Compound 21 [ka] A solution of 4-phenyl-2-(pyridine-2-yl)quinoline (1.50 g, 5.6 mmol) and 1,3-diiodopropane (8.28 g, 28 mmol) in MeCN (100 mL) was heated under reflux for 3 days, after which the solvent was removed under reduced pressure. The residue was dissolved in warmed MeOH (100 mL) and added dropwise to a solution of NH4PF6 (9.12 g, 55.9 mmol) in water (100 mL) by filtration with stirring. The resulting precipitate was collected by filtration and washed with water. The solid was dissolved in water / MeOH (1 / 1, 150 mL) and added dropwise to a solution of NH4PF6 (9.12 g, 55.9 mmol) in water (150 mL) by stirring. The resulting precipitate was collected by filtration, washed with water (2 × 10 mL), and air-dried to obtain the title compound (1.16 g, 35%) as a pale yellow powder. 1 1H NMR (400MHz, DMSO-d6)δ H 2.82-2.96 (2H,m), 4.42-4.55 (1H,m), 4.60-4.72 (1H,m), 5.00-5.13 (1H,m), 5.78-5.89 (1H,m), 7.72-7.82 (5H,m), 8.16 (1H,ddd,J=0.7,6.9 and 8.6Hz), 8.40 (1H,dd,J=1.4 and 8.6Hz), 8.4 6 (1H,ddd, J=1.4, 6.9 and 9.1Hz), 8.52-8.57 (2H,m), 8.79 (1H,app.dd, J=1.5 and 8.0Hz), 8.94 (1H,app.d, J=9.2Hz), 8.99 (1H,app.dt, J=1.4 and 8.0Hz), and 9.39 (1H,app.dd, J=1.3 and 6.1Hz); 19 F NMR (376 MHz, DMSO-d6) δ F -69.98 (d, J=710Hz); 13 ¹³C NMR (100 MHz, DMSO-d6) δ C30.96, 50.49, 56.47, 120.00, 126.35, 128.93, 129.04, 129.92, 130.71, 131.57, 131.75, 131.97, 132.65, 134.94, 137.46, 140.24, 144.78, 147.07, 147.58, 148.50, and 159.38.

[0158] 2-(pyridine-2-yl)benzothiazole [ka] A solution of 2-aminothiophenol (3.50 g, 28 mmol) and pyridine-4-carboxyaldehyde (3.00 g, 28 mmol) in EtOH (50 mL) was vigorously stirred (vortexed) in air for 6 hours. The amount of solvent was reduced, and the separated solid was heated to dissolve. The mixture was allowed to cool, and by filtration, the title compound (4.40 g, 74%) was obtained as beige needle-shaped crystals,δ H (CDCl3, 400MHz) 7.36-7.45 (2H, m), 7.51 (1H, ddd, J=1.0, 7.3 and 8.0Hz), 7.85 (1H, ddd, J=1.6, 7.6 and 7.8Hz), 7.96 (1H, ddd, J=0.6, 1.1 and 8.0Hz), 8.10 (1H, app.br.d, J=8.2Hz), 8.38 (1H, app.br.d, J=8.0Hz) and 8.69 (1H, app.br.d, J=4.8Hz); δ C (CDCl3, 100MHz) 120.79, 122.05, 123.60, 125.31, 125.68, 126.31, 136.13, 137.06, 149.69, 151.29, 154.29, and 169.41.

[0159] 6,7-Dihydrobenzothiazolo[3,2-a]pyrido[2,1-c]pyrazine-5,8-diiumbis(hexafluorophosphate)-compound 22: [ka] A mixture of 2-(pyridine-2-yl)benzothiazole (1.86 g, 8.8 mmol) in dibromoethane (10 mL) was heated under reflux for 16 hours, cooled, and filtered. The solution was then heated under reflux for 24 hours, cooled, and filtered again. The filters were combined, washed with Et2O (2 × 10 mL), triturated with hot MeOH (3 mL), cooled, and the resulting solid was filtered to obtain 6,7-dihydrobenzothiazolo[3,2-a]pyrido[2,1-c]pyrazine-5,8-diium dibromide (0.99 g) as a yellow powder. This yellow powder was dissolved in water (30 mL) and added dropwise with stirring to a solution of NH4PF6 (4.81 g, 29.5 mmol) in water (50 mL). The mixture was stirred for 0.5 hours, the precipitate was filtered, washed with water (2 × 20 mL), and air-dried to obtain the title compound (1.54 g, 33%) as a sage-green powder. δ H [(CD3)2CO,600MHz] 5.64-5.74(2H,m),5.74-5.74(2H,m),8.02(1H,app.t,J=7.5Hz),8.11(1H,ddd,J=1.1,7.3 and 8.5Hz),8. 53-8.68(3H,m),8.03(1H,app.t,J=7.9Hz),9.21(1H,app.d,J=7.9Hz) and 9.55(1H,app.br.d,J=6.0Hz);δ F [(CD3)2CO,470MHz] -72.55(d,J=710Hz);δ C [(CD3)2CO, 125MHz] 45.36, 53.68, 117.82, 125.47, 130.19, 131.42, 131.87, 132.03, 132.70, 136.62, 141.09, 148.83 and 159.55.

[0160] Evaluation of the redox potential and absorption spectrum of the compound of the present invention. Method for measuring oxidation-reduction potential The redox potential of a compound is measured using cyclic voltammetry with three electrodes.

[0161] The following three electrodes will be used: • One platinum fabrication electrode • One platinum auxiliary electrode or counter electrode A single platinum reference electrode immersed in a solution of 0.01 M AgNO3 + 0.1 M TBAP (tetrabutylammonium perchlorate) in acetonitrile.

[0162] The potential scan rate is fixed at 100 mV / s. E1 red This corresponds to the first reduction peak of the analyte. E2 red This corresponds to the second reduction peak of the analyte. E1 1 / 2 This corresponds to the redox potential of the oxidizing agent / reducing agent system, which is calculated as follows. E1 1 / 2 =(E1 red +E1 ox ) / 2 Here, E1 ox This corresponds to the first oxidation peak of the analyte compound. ΔE red E1 is calculated as follows: red and E2 red It corresponds to. ΔE red =│E2 red │-│E1 red │.

[0163] The displayed potential value is the initial reduction potential of the compound, relative to the standard hydrogen reference electrode (SHE).

[0164] The analytical solution contains 0.005 M of the analyte compound and 0.25 M of TBABF4 salt, with propylene carbonate as the solvent.

[0165] Method for measuring absorption spectra This solution is introduced into a quartz cell, and at least one working electrode in the form of a platinum grid is placed on it. The analyte compound is then colored on this electrode. The time-domain absorption spectrum of the analyte compound is measured by ultraviolet-visible spectroscopy.

[0166] The results for each synthesized compound are shown in Table 1 below. E1red This corresponds to the first reduction potential. The colors shown in Table 1 are the visual colors perceived by an emmetropic eye under daylight conditions. λ max Please note that the values ​​are only approximate indicators of the color of a particular compound. However, due to the broad range of absorption bands, the entire absorption spectrum must be considered to understand the final color of a compound.

[0167] For comparison, Table 2 shows the results obtained for seven known compounds (comparative compounds).

[0168] Comparing the known compound (comparison compound) COMP2 (green) with the novel compound 17 (red), it can be seen that the color changed from green to red by introducing a diazine ring into the structure. In the activated state, the molecule is red, not green.

[0169] Comparing the known compounds COMP3 (blue) and COMP7 (blue) with the novel compounds 16 (orange), 20 (transparent), and 18 (yellow), it can be seen that the effect of shifting the maximum absorption wavelength to a lower value can be obtained by introducing different groups such as diazines and triazines, either individually or by including them in more complex molecular structures. These groups can be introduced between two alkylbipyridinium groups or by substituting the central pyridinium group of a terpyridinium molecule. The molecules thus obtained are yellow, orange, red, green, or purple, rather than blue.

[0170] The known compound COMP4, which contains a phenyl group between two alkylbipyridinium groups, was also observed to be orange in color and to have an activation potential of -1.21V. The novel molecule according to the present invention has a much lower activation potential than this known compound COMP4.

[0171] Furthermore, it was observed that the already known compounds (comparative compounds) 5 and 6, although containing two nitrogen atoms, exhibited a lower degree of aromaticity or conjugation than the novel compounds 16 and 17. Comparative compounds 5 and 6 are blue molecules in their activated state, while novel compound 16 is orange and novel compound 17 is red.

[0172] [Table 5]

[0173] [Table 6]

[0174] [Table 7]

[0175] [Table 8]

[0176] [Table 9]

[0177] [Table 10]

[0178] [Table 11]

[0179] [Table 12]

[0180] [Table 13]

[0181] [Table 14]

[0182] The present invention further relates to the following embodiments: 1. Electrochromic polycyclic compounds represented by formula (I): [ka] (In the formula, A is N, N-R1, or + It is N-R1; B is either C-R2 or N; D is N, N-R4 or + It is N-R4; F may or may not exist, and if it exists, it is -CH2-; R1 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R2 is an aryl that may be optionally substituted with H; R3 is H, C1~C 18 Alkyl, optionally substituted aryl, or optionally substituted heteroaryl, such as Z or -CH2-aryl; R4 is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; And / or R5 and R6 together may form an optionally substituted aromatic hydrocarbon ring, e.g., a variant of a condensed ring such as arylene, e.g., benzene, or naphthalene, condensed around the central nitrogen-containing heteroring to which they are bonded, or an optionally substituted heteroaromatic ring, e.g., thiophene, selenofene, pyridine, pyridinium, the aromatic hydrocarbon ring or substituted heteroaromatic ring may be optionally substituted, e.g., with at least one Y or one or two Z; And / or R3 and R4 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridine, pyridinium, pyrimidine, pyrimidinium, pyridazine, pyridazinium, pyrazine, pyrazinium, or an optionally substituted bicyclic aromatic ring containing one or more nitrogen atoms, e.g., quinolinium or benzimidazolium, wherein the aromatic ring is substituted with, for example, at least one Y; And / or R1 and R2 together may form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, condensed around the central nitrogen-containing heteroring to which they are bonded, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; And / or R2 and R3 together may form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, an optionally substituted aromatic hydrocarbon ring, or an optionally substituted nitrogen-containing nonaromatic ring, e.g., a 7-membered ring, a saturated diazepine, condensed around the central nitrogen-containing heteroring to which they are bonded, wherein the ring is substituted with, for example, at least one Y; Z is [ka] and; Y is C1~C 18 Alkyl, optionally substituted aryl, or -CH2-aryl; n is chosen to balance the number of positive charges, and n is at least 2; X is an anion or a mixture thereof; [ka] It is either a single bond or a double bond; However, the nitrogen-containing heteroring at the center contains at least two double bonds; and The electrochromic polycyclic compound includes at least two rings (whether or not they are fused with the central nitrogen-containing heteroring), in addition to the central nitrogen-containing heteroring, provided that at least one of the two rings is a nitrogen-containing ring. 2. R1 and R2 together form a nitrogen-containing aromatic ring, or a bicyclic aromatic ring containing one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, wherein the aromatic ring is condensed with the central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is C1-C6 alkyl or C6-C 10 The electrochromic polycyclic compound of formula (I) according to embodiment 1, wherein the aryl group may be optionally substituted with 1 to 3 Y groups selected from aryl groups, and the aryl group may be optionally substituted with a C1-C6 haloalkyl or C1-C6 alkoxy group. 3. R3 and R4 together form a nitrogen-containing aromatic ring, or a bicyclic aromatic ring containing one or more nitrogen atoms, and the aromatic ring is condensed with a central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is C1-C6 alkyl or C6-C 10The electrochromic polycyclic compound of formula (I) according to embodiment 1 or 2, wherein the aryl group may be optionally substituted with 1 to 3 Y groups selected from aryl groups, and the aryl group may be optionally substituted with a C1-C6 haloalkyl or C1-C6 alkoxy group. 4. R2 is H or C6~C 10 It is an aryl, and the C6~C 10 An electrochromic polycyclic compound of formula (I) according to embodiment 1 or 3, wherein the aryl group may be optionally substituted with a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 alkoxy group. 5. R3 is C6~C 10 Aryl or Z: [ka] And Y is C1~C 18 Alkyl, C6~C 10 It is an aryl, and the C6~C 10 An electrochromic polycyclic compound of formula (I) according to any one of embodiments 1, 2, or 4, wherein the aryl group may be optionally substituted with 1 to 3 groups selected from C1 to C6 alkyl groups. 6. R5 and R6 together form an aromatic hydrocarbon ring or heteroaromatic ring, and the aromatic hydrocarbon ring or heteroaromatic ring is condensed with a central nitrogen-containing heteroaromatic ring to which they are bonded, and the aromatic hydrocarbon ring or heteroaromatic ring has one or two Z: [ka] (Y is -CH2-(C6~C 10 An electrochromic polycyclic compound of formula (I) according to any one of embodiments 1 to 5, which may be optionally substituted with aryl(I). 7. R5 is H, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10An electrochromic polycyclic compound of formula (I) according to any one of embodiments 1 to 5, wherein the aryl or heteroaryl is optionally substituted with 1 to 3 groups selected from Hal, C1-C6 alkyl, or C1-C6 haloalkyl. 8. R6 is H, C6~C 10 It is an aryl, and the aryl is a C1-C6 alkyl, a C1-C6 haloalkyl, or a C6-C 10 It is optionally substituted with 1 to 3 groups selected from the aryl group, or R6 is Z: [ka] That is (Y is C1~C 18 Alkyl, C6~C 10 An electrochromic polycyclic compound of formula (I) according to any one of embodiments 1 to 5 and 7, wherein the aryl is optionally substituted with 1 to 3 groups selected from C1 to C6 alkyl groups. 9. The compound is of formula (III): [ka] (In the formula, B is C-R2; R1 and R2 together form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, wherein the aromatic ring is substituted, for example, with at least one Y, e.g., an optionally substituted aryl; R5, R6, R 5’ , R 6’ (where Z, Y, n and X are as defined in claim 1) An electrochromic polycyclic compound of formula (I) as described in embodiment 3, represented by [formula]. 10. R1 and R2 together form pyridinium, quinolinium, benzothiazolium, or benzimidazolium, and the aromatic groups are condensed on the central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is C1-C6 alkyl or C6-C 10 The electrochromic polycyclic compound of formula (I) according to embodiment 9, wherein the aryl group may be optionally substituted with 1 to 3 Y groups selected from aryl groups, and the aryl group may be optionally substituted with a C1-C6 haloalkyl or C1-C6 alkoxy group. 11. Equations (IIIa), (IIIb), (IIIc), and (IIId): [ka] (In these formulas, R5 is H, C1~C 18 Alkyl, C1-C 18 The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R6 is H, C1~C 18 The alkyl, optionally substituted aryl, optionally substituted heteroaryl, or Z; R 5’ and R 6’ It may or may not exist, and if it exists, both are H; W is NY, S, O, or Se; Z, Y, [ka] (where , n, and X are as defined in Embodiment 1) An electrochromic polycyclic compound of formula (I) as described in embodiment 9 or 10, represented by any one of the following. 12. An electrochromic polycyclic compound of formula (I) according to any one of embodiments 9 to 11, wherein R5 is selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy, phenyl, or thienyl, and the phenyl may be optionally substituted with 1 to 3 groups selected from Hal, C1-C6 alkyl, or C1-C6 haloalkyl. 13. R6 is H, phenyl, naphthyl, biphenyl, or thienyl, and the phenyl is C1-C6 alkyl, C1-C6 haloalkyl, or C6-C 10 An electrochromic polycyclic compound of formula (I) according to any one of embodiments 9 to 12, which may be optionally substituted with 1 to 3 groups selected from aryl groups. 14. The compound is of formula (IV): [ka] (In the formula, B is either C-R2 or N; R2 is H or an optionally substituted aryl; preferably H or phenyl; R3 is an aryl or Z which may be optionally substituted; R5 is H; R6 is Z; Alternatively, R5 and R6 may together form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, e.g., arylene, e.g., benzene, which is fused to the central nitrogen-containing six-membered heteroring to which they are bonded, and the heteroaromatic ring or aromatic hydrocarbon ring is substituted, for example, with at least Y or one or two Z; Z, Y, n, and X are as defined in Embodiment 1. An electrochromic polycyclic compound of formula (I) as described in Embodiment 1, represented by [formula]. 15. Equation (VI) or Equation (VII): [ka] (In these formulas, R2 is an aryl that may be optionally substituted with H; R3 is H, an aryl that may be optionally substituted, or Z; Z, Y, n, and X are as defined in Embodiment 1. An electrochromic polycyclic aromatic compound of formula (IV) as described in embodiment 14, represented by [formula]. 16. Y is -CH2-(C6~C 10 An electrochromic polycyclic aromatic compound of formula (I) as described in embodiment 14, which is an aryl compound. 17. An electrochromic polycyclic aromatic compound of formula (I) according to embodiment 15 or 16, wherein both R2 and R3 are phenyl. 18. Formula (V): [ka] (In the formula, B is either CH or N; Z, Y, and X are as defined in Embodiment 1. An electrochromic polycyclic compound of formula (IV) as described in embodiment 14, represented by [formula]. 19. An electrochromic polycyclic compound of formula (V) as described in embodiment 18, wherein B is CH. 20. R6 is Z [ka] (In the formula, Y is n-hexyl or toryl) An electrochromic polycyclic compound of formula (I) as described in embodiment 18 or 19. 21. Formula (IX): [ka] (In the formula, B is C-R2; R3 and R4 together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium or benzimidazolium, which is condensed around the central nitrogen-containing seven-membered heteroring to which they are joined, and the aromatic ring is substituted with, for example, at least one Y, and preferably the aromatic ring is unsubstituted; R1 and R2 together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, quinolinium, or benzimidazolium, which is condensed around the central nitrogen-containing seven-membered heteroring to which they are joined, and which may be substituted with an optionally substituted aryl; R2 and R3 may together form an optionally substituted nitrogen-containing non-aromatic ring, such as a 7-membered ring or saturated diazepine, condensed around the central nitrogen-containing 7-membered heteroring to which they are joined, and the non-aromatic ring is preferably unsubstituted; Y, n, and X are as defined in Embodiment 1. An electrochromic polycyclic compound of formula (I) as described in Embodiment 1, represented by [formula]. 22. An electrochromic polycyclic compound of formula (I) according to embodiment 21, wherein R3 and R4 together form a heteroaromatic group selected from pyridinium or benzimidazolium, and the heteroaromatic group is condensed on a central nitrogen-containing 7-membered heteroring to which they are bonded. 23. An electrochromic polycyclic compound of formula (I) according to embodiment 21 or 22, wherein R1 and R2 together form a heteroaromatic group selected from pyridinium, quinolinium, or benzimidazolium, the heteroaromatic group is condensed on a central nitrogen-containing 7-membered heteroring to which they are bonded, and the heteroaromatic group may be optionally substituted with a phenyl group. 24. An electrochromic polycyclic compound of formula (I) according to any one of embodiments 21 to 23, wherein R2 and R3 together form a saturated diazepine condensed on a central nitrogen-containing heteroring to which they are bonded. 25. An electrochromic polycyclic compound of formula (I) as described in any one of embodiments 1 to 24, wherein n is 2. 26. An electrochromic polycyclic compound of formula (I) according to any one of embodiments 1 to 25, wherein the counterion X- is selected from halides, preferably fluorides and chlorides, tetrafluoroborates, tetraphenylborates, hexafluorophosphates, nitrates, methanesulfonates, trifluoromethanesulfonates, toluenesulfonates, hexachloroantimonates, bis(trifluoromethanesulfonyl)imides, perchlorates, acetates, and sulfates, or any mixture thereof. 27. X - An electrochromic polycyclic compound of formula (I) according to embodiment 26, wherein is a tetrafluoroborate or hexafluorophosphate. 28. An electrochromic polycyclic compound of formula (I) described in Embodiment 1, selected from the following:

[0183] [Table 15]

[0184] [Table 16]

[0185] [Table 17]

[0186] [Table 18]

[0187] 29. An electrochromic composition comprising at least one electrochromic polycyclic compound described in any one of embodiments 1 to 28 and a host medium. 30. The electrochromic composition according to embodiment 29, further comprising a host medium which is a fluid, a liquid crystalline medium, or a gel. 31. The electrochromic composition according to embodiment 29 or 30, wherein the host medium is selected from the group consisting of organic solvents, liquid crystals, polymers, liquid crystal polymers, and mixtures thereof. 32. The electrochromic composition according to embodiment 31, wherein the organic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, acetonitrile, propionitrile, benzonitrile, glutaronitrile, methylglutaronitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane, benzene, toluene, methyl ethyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, 2-methoxyethyl ether, xylene, cyclohexane, 3-methylcyclohexanone, ethyl acetate, ethyl phenylacetate, tetrahydrofuran, methanol, methyl propionate, ethylene glycol, ethylene carbonate, ionic liquid, and mixtures thereof. 33. The electrochromic composition according to embodiment 31 or 32, wherein the host medium is a mixture of a liquid crystal polymer and an organic solvent. 34. The electrochromic composition according to embodiment 31, wherein the polymer is selected from the group consisting of acrylate polymers, polyurethanes, polyethylene oxides, polypropylene oxides, polyvinyl acetates, poly(N-vinylpyrrolidone), and polyvinylidene fluoride. 35. An electrochromic device comprising at least one electrochromic polycyclic compound described in any one of embodiments 1 to 28, or an electrochromic composition described in any one of embodiments 29 to 34. 36. An electrochromic device according to embodiment 35, which is an optical article, preferably selected from optical lenses or optical filters, windows, particularly windows of aircraft, automobiles or buildings, visors, mirrors, head-mounted devices and display elements, more preferably selected from optical lenses, most preferably selected from ophthalmic lenses. 37. The electrochromic device according to embodiment 36, wherein the ophthalmic lens is a corrective or non-corrective lens. 38. The electrochromic device according to embodiment 36 or 37, wherein the ophthalmic lens is selected from the group consisting of contact lenses, intraocular lenses, sunglasses, ski goggles, magnifying lenses, protective lenses, and visors. 39. The electrochromic device according to embodiment 36, wherein the display element is a screen or a monitor. 40. The electrochromic device according to embodiment 36, wherein the window is selected from the group consisting of automobile windows, ship windows, aircraft windows, building windows, and variable transmittance devices. 41. An electrochromic device according to embodiment 35, comprising a pair of opposing substrates having a gap for containing a mixture of a host medium and at least one electrochromic polycyclic compound according to any one of embodiments 1 to 28 or an electrochromic composition according to any one of embodiments 29 to 34, and a frame for holding the pair of substrates adjacent to each other. 42. An electrochromic device according to embodiment 35, comprising an optical component having at least one array of transparent cells arranged parallel to the surface, wherein each cell is sealed and contains at least one electrochromic polycyclic compound according to any one of embodiments 1 to 28 or an electrochromic composition according to any one of embodiments 29 to 34.

Claims

1. Equation (I): 【Chemistry 1】 (In the formula, A is N, N-R １ , or ＋ N-R １ And; B is C-R ２ or N; D is N, N-R ４ , or ＋ N-R ４ And; F may or may not exist, and if it exists, it is -CH ２ - and; R １ is C １ to C １８ alkyl, optionally substituted aryl, or -CH ２ -aryl; R ２ is an aryl that may be optionally substituted with H; R ３ H, C １ ~C １８ Alkyl, optionally substituted aryl, or optionally substituted heteroaryl, such as Z or -CH ２ - is an allele; R ４ C １ ~C １８ Alkyl, optionally substituted aryl, or -CH ２ - is an allele; R ５’ and R ６’ It may or may not exist, and if it exists, both are H; R ５ H, C １ ~C １８ Alkyl, C １ ~C １８ The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R ６ is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; and / or R ５ and R ６ They may together form optionally substituted aromatic hydrocarbon rings, such as arylenes, benzenes, or naphthalenes, which are condensed around the central nitrogen-containing heteroring to which they are bonded, or optionally substituted heteroaromatic rings, such as thiophenes, selenofenes, pyridines, or pyridiniums, which may be optionally substituted by, for example, at least one Y or one or two Zs; and / or R ３ and R ４ They may together form an optionally substituted nitrogen-containing aromatic ring, such as pyridine, pyridinium, pyrimidine, pyrimidinium, pyridazine, pyridazinium, pyrazine, pyrazinium, or an optionally substituted bicyclic aromatic ring containing one or more nitrogen atoms, such as quinolinium or benzimidazolium, which is fused to the central nitrogen-containing heteroring to which they are bonded, and the aromatic ring is substituted with, for example, at least one Y; and / or R １ and R ２ They may together form an optionally substituted nitrogen-containing aromatic ring, e.g., pyridinium, or an optionally substituted bicyclic aromatic ring, e.g., quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, condensed around a central nitrogen-containing heteroring to which they are bonded, wherein the aromatic ring is substituted with, for example, at least one Y, e.g., an optionally substituted aryl; and / or R ２ and R ３ They may together form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, optionally substituted aromatic hydrocarbon ring, or optionally substituted nitrogen-containing nonaromatic ring, e.g., a 7-membered ring, or a saturated diazepine, which is fused to the central nitrogen-containing heteroring to which they are bonded, and the ring is substituted with, for example, at least one Y; Z is, 【Chemistry 2】 And; Y is C １ ~C １８ Alkyl, optionally substituted aryl, or -CH ２ - is an allele; n is chosen to balance the number of positive charges, and n is at least 2; X is an anion or a mixture thereof; 【Transformation 3】 It is either a single bond or a double bond; However, the central nitrogen-containing heteroring contains at least two double bonds; and The electrochromic polycyclic compound includes at least two rings (whether or not they are fused with the central nitrogen-containing heteroring) in addition to the central nitrogen-containing heteroring, provided that at least one of the two rings is a nitrogen-containing ring. An electrochromic polycyclic compound represented by [formula].

2. The aforementioned compound is of formula (II): 【Chemistry 4】 (In the formula, A is N or ＋ N-R １ And; B is C-R ２ or N; D is N or ＋ N-R ４ And; R １ C １ ~C １８ Alkyl, optionally substituted aryl, or -CH ２ - is an allele; R ２ is an aryl that may be optionally substituted with H; R ３ H, C １ ~C １８ Alkyl, optionally substituted aryl, optionally substituted heteroaryl, e.g., Z or -CH ２ - is an allele; R ４ C １ ~C １８ Alkyl, optionally substituted aryl, or -CH ２ - is an allele; R ５’ and R ６’ It may or may not exist, and if it exists, both are H; R ５ H, C １ ~C １８ Alkyl, C １ ~C １８ The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R ６ is H, an optionally substituted aryl, an optionally substituted heteroaryl, or Z; and / or R ５ and R ６ They may together form an optionally substituted aromatic hydrocarbon ring, e.g., arylene, e.g., benzene, or an optionally substituted heteroaromatic ring, e.g., thiophene, selenofene, pyridine, pyridinium, which is condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and the aromatic hydrocarbon ring or heteroaromatic ring may be optionally substituted with, for example, at least one Y, one Z, or two Z; and / or R ３ and R ４ They may together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, or an optionally substituted bicyclic aromatic ring, such as quinolinium or benzimidazolium, containing one or more nitrogen atoms, condensed around a central nitrogen-containing six-membered heteroring to which they are bonded, wherein the aromatic ring is substituted, for example, with at least one Y, and for example, with an optionally substituted aryl; and / or R １ and R ２ They may together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, or an optionally substituted bicyclic aromatic ring, such as quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, condensed around a central nitrogen-containing six-membered heteroring to which they are bonded, wherein the aromatic ring is substituted with, for example, at least one Y, for example, an optionally substituted aryl; and / or R ２ and R ３ They combine to form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, which is condensed around the central nitrogen-containing six-membered heteroring to which they are bonded, and is, for example, substituted with at least one Y; However, the electrochromic polycyclic compound includes at least two rings in addition to the central nitrogen-containing six-membered heteroring (whether or not it is fused to the central nitrogen-containing six-membered heteroring), provided that at least one of the two rings is a nitrogen-containing ring; Z, Y, 【Transformation 5】 、 An electrochromic polycyclic compound according to claim 1, represented as n and X are as defined in claim 1.

3. The aforementioned compound is of formula (III). 【Transformation 6】 (In the formula, B is C-R ２ And; R １ and R ２ They may together form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, or an optionally substituted bicyclic aromatic ring, such as quinolinium, benzimidazolium, benzothiazolium, benzoselenazolium, or benzoxazolium, comprising one nitrogen atom and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, and selenium, condensed around a central nitrogen-containing six-membered heteroring to which they are bonded, wherein the aromatic ring is substituted with, for example, at least one Y, for example, an optionally substituted aryl; R ５ H, C １ ~C １８ Alkyl, C １ ~C １８ The alkoxy, optionally substituted aryl, or optionally substituted heteroaryl; R ６ H, C １ ~C １８ The alkyl, optionally substituted aryl, optionally substituted heteroaryl, or Z; R ５’ and R ６’ It may or may not exist, and if it exists, both are H; Z, Y, 【Transformation 7】 (where n and X are as defined in claim 1) An electrochromic polycyclic compound according to claim 1 or 2, represented by [the formula shown in the original text].

4. Formulas (IIIa), (IIIb), (IIIc), and (IIId): 【Transformation 8】 (In the formula, R ５ is H, C １ ~C １８ alkyl, C １ ~C １８ alkoxy, aryl which may be optionally substituted, or heteroaryl which may be optionally substituted; R ６ H, C １ ~C １８ The alkyl, optionally substituted aryl, optionally substituted heteroaryl, or Z; R ５’ and R ６’ either exist or do not exist, and if they exist, they are both H; W is N-Y, S, O, or Se; Z, Y, 【Chemistry 9】 (where n and X are as defined in claim 1) An electrochromic polycyclic compound according to any one of claims 1 to 3, represented by any one of the following:

5. The aforementioned compound is of formula (IV): 【Chemistry 10】 (In the formula, B is C-R ２ or N; R ２ is H or an optionally substituted aryl; preferably H or phenyl; R ３ is an aryl or Z which may be optionally substituted; R ５ is H; R ６ Is it Z? or R ５ and R ６ However, together they may form an optionally substituted heteroaromatic ring, e.g., thiophene, pyridinium, or optionally substituted aromatic hydrocarbon ring, e.g., arylene, e.g., benzene, which is fused to the central nitrogen-containing six-membered heteroring to which they are bonded, and the heteroaromatic ring or aromatic hydrocarbon ring is substituted with, for example, at least Y or, for example, two Z; Z, Y, n, and X are as defined in claim 1. An electrochromic polycyclic compound according to claim 1 or 2, represented by [the formula shown in the original text].

6. Formula (V): 【Chemistry 11】 (In the formula, B is either CH or N; Z, Y, and X are as defined in claim 1. An electrochromic polycyclic compound of formula (IV) according to claim 5, represented by [formula].

7. An electrochromic polycyclic compound of formula (V) according to claim 6, wherein B is CH.

8. Formula (VI) or Formula (VII): 【Chemistry 12】 (In these formulas, R ２ is an aryl that may be optionally substituted with H; R ３ is H, an aryl that may be optionally substituted, or Z; Z, Y, n, and X are as defined in claim 1. An electrochromic polycyclic aromatic compound of formula (IV) according to claim 5, represented by [formula].

9. Formula (IX) 【Chemistry 13】 (In the formula, B is C-R ２ And; R ３ and R ４ Together, they form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium or benzimidazolium, which is condensed around the central nitrogen-containing seven-membered heteroring to which they are bonded, and the aromatic ring is substituted with, for example, at least one Y, preferably the aromatic ring is unsubstituted; R １ and R ２ They combine to form an optionally substituted nitrogen-containing aromatic ring, such as pyridinium, quinolinium, or benzimidazolium, which is fused to the central nitrogen-containing seven-membered heteroring to which they are bonded, and which may be substituted with an optionally substituted aryl; R ２ and R ３ They may together form an optionally substituted nitrogen-containing non-aromatic ring, such as a seven-membered ring or saturated diazepine, which is condensed around the central nitrogen-containing seven-membered heteroring to which they are bonded, and the non-aromatic ring is preferably unsubstituted; Y, n, and X are as defined in claim 1. The electrochromic polycyclic compound according to claim 1, represented by [the specified symbol].

10. The electrochromic polycyclic compound according to any one of claims 1 to 9, wherein the counterion X- is selected from halides, preferably fluorides and chlorides, tetrafluoroborates, tetraphenylborates, hexafluorophosphates, nitrates, methanesulfonates, trifluoromethanesulfonates, toluenesulfonates, hexachloroantimonates, bis(trifluoromethanesulfonyl)imides, perchlorates, acetates, and sulfates, or any mixture thereof.

11. The following: Table 1 Table 2 Table 3 Table 4 An electrochromic polycyclic compound according to any one of claims 1 to 10, selected from the above.

12. An electrochromic composition comprising at least one electrochromic polycyclic compound according to any one of claims 1 to 11 and a host medium.

13. The electrochromic composition according to claim 12, further comprising a host medium which is a fluid, a liquid crystalline medium, or a gel.

14. An electrochromic device comprising at least one electrochromic polycyclic compound according to any one of claims 1 to 11, or the electrochromic composition according to claim 12 or 13.

15. The electrochromic device according to claim 14, selected from an optical article; preferably an optical lens or optical filter; a window, particularly an aircraft or automobile or building window; a visor; a mirror; a head-mounted device; and a variable transmittance device; preferably the optical article is an optical lens, and most preferably the optical article is an ophthalmic lens.

Images