阅读说明：本技术 包含电致变色化合物的电致变色装置及其制造方法 (Electrochromic device comprising electrochromic compound and method for manufacturing the same ) 是由 林潽圭 李志永 金志勳 于 2018-07-04 设计创作，主要内容包括：本申请涉及电致变色装置和用于制造其的方法,所述电致变色装置包含由化学式1表示的用于电致变色的化合物。(The present application relates to an electrochromic device including a compound for electrochromic represented by chemical formula 1 and a method for manufacturing the same.)

1. an electrochromic device, comprising:

A substrate;

A first electrode formed on the substrate;

A second electrode disposed opposite to the first electrode;

An electrolyte layer formed between the first electrode and the second electrode; and

An electrochromic layer formed between the electrolyte layer and the second electrode,

Wherein one or more layers of the electrochromic layer comprise a compound for electrochromic according to the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the first and second,

ra and Rb are the same as or different from each other, and each independently is a group serving as an electron acceptor;

Y1 to Y5 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

Y6 and Y7 are different from each other and are each independently a direct bond, NR, O, SiRR ', PR, S, GeRR', Se, or Te;

a is 0 or 1;

When a is 0, Y6 is a direct bond, and Y7 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

When a is 1, Y7 is a direct bond, and Y6 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

n and m are each an integer of 0 to 5;

When n and m are 2 or more, the structures in parentheses are the same as or different from each other;

Z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR; and

R1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

2. The electrochromic device of claim 1, wherein chemical formula 1 is represented by chemical formula 2 or 3:

[ chemical formula 2]

[ chemical formula 3]

In the chemical formula 2 or 3, the metal oxide,

Ra and Rb are the same as or different from each other, and each independently is a group serving as an electron acceptor;

Y1 to Y7 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

n and m are each an integer of 0 to 5;

When n and m are 2 or more, the structures in parentheses are the same as or different from each other;

Z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR; and

R1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

3. the electrochromic device of claim 2, wherein chemical formula 3 is represented by the following chemical formula 1-1 or 1-2:

[ chemical formula 1-1]

[ chemical formulas 1-2]

in chemical formula 1-1 or chemical formula 1-2,

ra and Rb are the same as or different from each other, and each independently is a group serving as an electron acceptor;

Y1 to Y6 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR; and

R1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

4. The electrochromic device of claim 1, wherein Ra and Rb are the same or different from each other and are each any one of the following structures:

In the above-described structure, the first and second electrodes are formed on the substrate,

c is an integer from 1 to 4;

When c is 2 or more, the structures in two or more brackets are the same as or different from each other; and

R10 to R13 are the same as or different from each other, and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group, Or a substituted or unsubstituted heteroaryl.

5. The electrochromic device of claim 1, wherein R1 and R2 are the same or different from each other and are each independently hydrogen, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

6. the electrochromic device of claim 1, wherein R1 and R2 are hydrogen.

7. The electrochromic device of claim 1, wherein Z1-Z4 are the same or different from each other and are each independently SR, and R is a substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl.

8. The electrochromic device of claim 1, wherein chemical formula 1 is represented by any one of the following chemical formulae 1-11 to 1-19:

[ chemical formulas 1 to 11]

[ chemical formulas 1 to 12]

[ chemical formulas 1 to 13]

[ chemical formulas 1 to 14]

[ chemical formulas 1 to 15]

[ chemical formulas 1 to 16]

[ chemical formulas 1 to 17]

[ chemical formulas 1 to 18]

[ chemical formulas 1 to 19]

In chemical formulas 1-11 to 1-19,

Y1 to Y7 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

Z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR; and

r, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, or a substituted or unsubstituted heterocyclic group.

9. The electrochromic device of claim 1, wherein chemical formula 1 is represented by any one of the following compounds:

10. The electrochromic device of claim 1, wherein the electrochromic layer has a thickness greater than or equal to 20nm and less than or equal to 1 μ ι η.

11. A method for fabricating an electrochromic device, comprising:

Preparing a substrate;

Forming a first electrode on the substrate;

forming a second electrode opposite to the first electrode;

Forming an electrolyte layer between the first electrode and the second electrode; and

Forming an electrochromic layer between the electrolyte layer and the second electrode,

Wherein one or more layers of the electrochromic layer comprise a compound for electrochromic according to the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the first and second,

Ra and Rb are the same as or different from each other, and each independently is a group serving as an electron acceptor;

Y1 to Y5 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

Y6 and Y7 are different from each other and are each independently a direct bond, NR, O, SiRR ', PR, S, GeRR', Se, or Te;

a is 0 or 1;

When a is 0, Y6 is a direct bond and Y7 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

When a is 1, Y7 is a direct bond and Y6 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

n and m are each an integer of 0 to 5;

When n and m are 2 or more, the structures in parentheses are the same as or different from each other;

Z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR; and

R1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

12. the method for manufacturing an electrochromic device according to claim 11, wherein a method of forming the electrochromic layer is a solution method.

Technical Field

this application claims priority and benefit to korean patent application No. 10-2017-0087179, filed on 10.7.7.2017 with the korean intellectual property office, the entire contents of which are incorporated herein by reference.

The present application relates to electrochromic devices comprising compounds for electrochromic.

background

The electrochromic technology is a technology that changes the color of a material using an electrochemical reaction, and refers to a characteristic in which the color of a material reversibly changes when an electron density changes with the intercalation or deintercalation of cations in an electrode structure due to an electrochemical redox reaction occurring by a change in an applied voltage.

An electrochromic device is a device having a color change by an electrochemical reaction. When a potential difference occurs in the electrochromic device due to external electrical stimulation, ions or electrons contained in the electrolyte migrate into the electrochromic layer, causing a redox reaction. The color of the electrochromic device is changed by the redox reaction of the electrochromic layer. The reductive electrochromic material means a material that is colored when a reduction reaction (cathode reaction) occurs and is discolored when an oxidation reaction (anode reaction) occurs. The oxidative electrochromic material means a material that is colored when an oxidation reaction occurs and discolored when a reduction reaction occurs.

Electrochromic devices have been actively studied in applications such as optical shutters, displays, smart windows, or electrochromic mirrors for automobiles, due to exhibiting high contrast, simple transmittance control by driving voltage, low driving voltage, bistability, and wide viewing angle.

Disclosure of Invention

Technical problem

the present application relates to providing an electrochromic device including a compound for electrochromic having excellent stability.

Technical scheme

One embodiment of the present application provides an electrochromic device, including: a substrate; a first electrode formed on the substrate; a second electrode disposed opposite to the first electrode; an electrolyte layer formed between the first electrode and the second electrode; and an electrochromic layer formed between the electrolyte layer and the second electrode, wherein one or more layers of the electrochromic layer include a compound for electrochromic according to the following chemical formula 1.

[ chemical formula 1]

In the chemical formula 1, the first and second,

Ra and Rb are the same as or different from each other, and each independently is a group serving as an electron acceptor;

Y1 to Y5 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te;

Y6 and Y7 are different from each other and are each independently a direct bond, NR, O, SiRR ', PR, S, GeRR', Se, or Te;

a is 0 or 1;

When a is 0, Y6 is a direct bond and Y7 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

When a is 1, Y7 is a direct bond and Y6 is CRR ', NR, O, SiRR ', PR, S, GeRR ', Se, or Te;

n and m are each an integer of 0 to 5;

When n and m are 2 or more, the structures in parentheses are the same as or different from each other;

z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR, SiRR ' R", PRR ', SR, GeRR ' R ", SeR OR TeR;

r1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, Substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

Another embodiment of the present application provides a method for manufacturing an electrochromic device, including: preparing a substrate; forming a first electrode on a substrate; forming a second electrode opposite to the first electrode; forming an electrolyte layer between the first electrode and the second electrode; and forming an electrochromic layer between the electrolyte layer and the second electrode, wherein one or more layers of the electrochromic layer include the compound for electrochromic according to chemical formula 1.

Advantageous effects

The compound for electrochromic according to one embodiment of the present application can introduce sulfur (S) or the like into an alkyl chain and enhance electron transfer through chalcogen-chalcogen interaction in a molecule, and thus can enhance an electrochromic response rate and electrochromic conversion efficiency (coloring efficiency).

The compound for electrochromic according to one embodiment of the present application has excellent oxidation stability and excellent lifetime when used in an electrochromic device.

Drawings

Fig. 1 is a side view of an electrochromic device according to one embodiment of the present application.

FIG. 2 is a graph showing the MS spectrum of Compound A-2.

Fig. 3 is a graph showing the MS spectrum of compound 1.

FIG. 4 is a graph showing the MS spectrum of Compound B-2.

FIG. 5 is a graph showing the MS spectrum of Compound B-3.

Fig. 6 is a graph showing the MS spectrum of compound 2.

Fig. 7 is a graph showing the UV spectrum of compound 3.

Fig. 8 is a graph showing the results of measuring CV of compound 3.

fig. 9 is a graph showing the MS spectrum of compound 3.

fig. 10 is a graph showing the experimental results in the electrochromic device of compound 3.

< reference character >

10: electrochromic device

20: a first electrode

30: electrolyte layer

40: electrochromic layer

50: second electrode

Detailed Description

Hereinafter, the present application will be described in more detail.

embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily practice the present disclosure. However, the present disclosure may be embodied in various different forms and is not limited to the embodiments described herein.

One embodiment of the present application provides an electrochromic device, including: a substrate; a first electrode formed on the substrate; a second electrode disposed opposite to the first electrode; an electrolyte layer formed between the first electrode and the second electrode; and an electrochromic layer formed between the electrolyte layer and the second electrode, wherein one or more layers of the electrochromic layer include the compound for electrochromic according to chemical formula 1.

In this specification, unless specifically stated to the contrary, a description of a part "comprising" certain components means that the other components can be further included, and is not exclusive of the other components.

In the present specification, the description that a certain member is placed "on" another member includes not only a case where one member abuts another member but also a case where another member exists between the two members.

In the present application, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from: deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a carbonyl group, an ester group, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkenyl group, a silyl group, a siloxane group, a boron group, an amine group, an arylphosphine group, a phosphine oxide group, an aryl group, and a heterocyclic group, or a substituent connected with two or more substituents among the above-exemplified substituents, or no substituent. For example, "a substituent to which two or more substituents are attached" may include a biphenyl group. In other words, biphenyl can be an aryl group, or interpreted as a substituent with two phenyl groups attached.

in the context of the present application, it is,meaning a site that is bonded to another substituent or bonding site.

In the present application, examples of the halogen group may include fluorine, chlorine, bromine, or iodine.

in the present application, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 30.

In the amide group, in the present application, the nitrogen of the amide group may be substituted with hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

in the present application, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 30.

in the present application, in the ester group, oxygen or carbon of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

In the present application, the alkyl group may be linear or branched, and although not particularly limited thereto, the number of carbon atoms is preferably 1 to 30. Specific examples thereof may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present application, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms. Specific examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

In the present application, alkoxy groups may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30. Specific examples thereof may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.

in the present application, the amine group may be selected from-NH₂An alkylamino group, an N-arylalkylamino group, an arylamino group, an N-arylheteroarylamino group, an N-alkylheteroarylamino group, and a heteroarylamino group, and although not particularly limited thereto, the number of carbon atoms is preferably 1 to 30. Specific examples of the amine group may include, but are not limited to, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a naphthylamino group, a biphenylamino group, an anthracylamino group, a 9-methyl-anthracylamino group, a diphenylamino group, an N-phenylnaphthylamino group, a xylylamino group, an N-phenyltolylamino group, a triphenylamino group, and the like.

In the present application, the alkyl groups in the alkylamino group, N-arylalkylamino group, alkylthio group, alkylsulfonyl group, and N-alkylheteroarylamino group are the same as the examples of the alkyl groups described above.

In the present application, the alkenyl group may be linear or branched, and although not particularly limited thereto, the number of carbon atoms is preferably 2 to 30. Specific examples thereof may include: vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (biphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.

in the present application, specific examples of the silyl group may include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like.

In the present application, the boron group may be-BR₁₀₀R₂₀₀And R is₁₀₀And R₂₀₀Are identical or different from each other and can each be independently selected from hydrogen; deuterium; halogen; a nitrile group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

in the present application, specific examples of the phosphine oxide group may include, but are not limited to, diphenylphosphineoxide, dinaphthylphospheoxide, and the like.

in the present application, the aryl group may be monocyclic or polycyclic.

when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Specific examples of the monocyclic aryl group may include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is notParticularly, but preferably 10 to 30. Specific examples of the polycyclic aromatic group may include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, and the like,A phenyl group, a fluorenyl group, and the like, but are not limited thereto.

In the present application, the aryl group in the aryloxy group, the arylthio group, the arylsulfonyl group, the N-arylalkylamino group, the N-arylheteroarylamino group, and the arylphosphino group is the same as the example of the aryl group described above.

In the present application, examples of arylamine groups include substituted or unsubstituted monoarylamine groups, substituted or unsubstituted diarylamine groups, or substituted or unsubstituted triarylamine groups. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. An arylamine group comprising two or more aryl groups can comprise a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the above-mentioned aryl groups.

In the present application, a heterocyclic group is a group containing one or more atoms other than carbon (i.e., heteroatoms), and in particular, the heteroatoms may include one or more atoms selected from O, N, Se, S, and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl group,Oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzobenzoxazinylAzolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, thiazolyl, isoquinoylazolyl group,Oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but is not limited thereto.

in the present application, examples of heteroarylamino groups include a substituted or unsubstituted monoheteroarylamino group, a substituted or unsubstituted diheteroarylamino group, or a substituted or unsubstituted triheteroarylamino group. Heteroarylamine groups comprising two or more heteroaryls may comprise a monocyclic heteroaryl, a polycyclic heteroaryl, or both a monocyclic heteroaryl and a polycyclic heteroaryl. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of heteroaryl groups described above.

In the present application, examples of the heteroaryl group in the N-arylheteroarylamino group and the N-alkylheteroarylamino group are the same as those of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamino group and the N-alkylheteroarylamino group are the same as those of the heteroaryl group described above.

in one embodiment of the present specification, n and m are each an integer of 0 to 5.

In one embodiment of the present specification, n and m are each an integer of 0 to 4.

In one embodiment of the present specification, n and m are each an integer of 0 to 3.

In one embodiment of the present specification, n and m are each an integer of 0 to 2.

In one embodiment of the present specification, n and m are each 0 or 1.

In one embodiment of the present specification, n and m are the same as each other and each is 0 or 1.

In one embodiment of the present specification, the compound represented by chemical formula 1 may be bilaterally symmetrical with respect to a benzene ring.

In one embodiment of the present specification, the compound represented by chemical formula 1 may be represented by chemical formula 2 or 3 below.

[ chemical formula 2]

[ chemical formula 3]

In the chemical formula 2 or 3, the metal oxide,

ra and Rb are the same or different from each other and each independently a group serving as an electron acceptor,

Y1 to Y7 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te,

n and m are each an integer of 0 to 5,

When n and m are 2 or more, the structures in parentheses are the same as or different from each other,

Z1 to Z4 are identical to OR different from one another and are each independently CRR 'R', NRR ', OR, SiRR' R ', PRR', SR, GeRR 'R', SeR OR TeR, and

R1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, A substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, the compound represented by chemical formula 3 may be represented by the following chemical formula 1-1 or chemical formula 1-2.

[ chemical formula 1-1]

[ chemical formulas 1-2]

In chemical formula 1-1 or chemical formula 1-2,

Ra and Rb are the same or different from each other and each independently a group serving as an electron acceptor,

Y1 to Y6 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te,

Z1 to Z4 are identical to OR different from one another and are each independently CRR 'R', NRR ', OR, SiRR' R ', PRR', SR, GeRR 'R', SeR OR TeR, and

r1, R2, R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted, A substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present description, Ra and Rb can be any of the following structures.

In the above-described structure, the first and second electrodes are formed on the substrate,

c is an integer of 1 to 4,

When c is 2 or more, the structures in two or more brackets are the same as or different from each other, and

R10 to R13 are the same as or different from each other, and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group, Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 and R2 are the same or different from each other and are each independently hydrogen, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 and R2 are hydrogen.

In one embodiment of the present specification, R10 to R13 are the same as or different from each other, and each is independently hydrogen, a halogen group, a nitrile group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R10 to R13 are the same as or different from each other, and each is independently hydrogen, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

in one embodiment of the present specification, R10 to R13 are the same or different from each other and are each independently hydrogen, or substituted or unsubstituted alkyl.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkyl.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

in one embodiment of the present specification, R10 is an alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R11 to R13 are hydrogen.

In one embodiment of the present specification, Ra and Rb are eachAnd R13 and c are the same as described above.

in one embodiment of the present specification, Ra and Rb are eachAnd R13 is hydrogen.

In one embodiment of the present specification, Ra and Rb are eachAnd R10 is the same as described above.

In one embodiment of the present specification, Ra and Rb are eachAnd R10 is an alkyl group having 1 to 10 carbon atoms.

in one embodiment of the present specification, chemical formula 1 may be represented by any one of the following chemical formulae 1-11 to 1-19.

[ chemical formulas 1 to 11]

[ chemical formulas 1 to 12]

[ chemical formulas 1 to 13]

[ chemical formulas 1 to 14]

[ chemical formulas 1 to 15]

[ chemical formulas 1 to 16]

[ chemical formulas 1 to 17]

[ chemical formulas 1 to 18]

[ chemical formulas 1 to 19]

in chemical formulas 1-11 to 1-19,

y1 to Y7 are identical to or different from one another and are each independently CRR ', NR, O, SiRR ', PR, S, GeRR ', Se or Te,

Z1 to Z4 are identical to OR different from one another and are each independently CRR 'R', NRR ', OR, SiRR' R ', PRR', SR, GeRR 'R', SeR OR TeR, and

R, R 'and R' are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aralkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group, a nitro group, an imide group, an amide group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, Y1 to Y7 are the same as or different from each other and are each independently CRR ', NR, O or S, and R' are the same as described above.

In one embodiment of the present specification, Y1 to Y7 are the same as or different from each other, and each is independently NR or S, and R is the same as described above.

In one embodiment of the present specification, Y1 to Y7 are S.

in one embodiment of the present specification, Z1 to Z4 are the same OR different from each other and are each independently CRR ' R ", NRR ', OR SR, and R, R ' and R" are the same as described above.

In one embodiment of the present specification, Z1 to Z4 are the same or different from each other and are each independently O or SR, and R is the same as described above.

In one embodiment of the present specification, Z1 to Z4 are the same or different from each other and are each independently SR, and R is the same as described above.

in one embodiment of the present specification, Z1 to Z4 are the same or different from each other and are each independently SR, and R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, Z1 to Z4 are the same or different from each other and are each independently SR, and R is an alkyl group substituted with a substituted or unsubstituted heterocyclic group, an alkyl group substituted with a substituted or unsubstituted aryl group, or a linear or branched alkyl group.

In one embodiment of the present specification, Z1 to Z4 are the same as or different from each other and are each independently SR, and R is an alkyl group substituted with an alkyl-substituted heterocyclic group, an alkyl group substituted with an alkyl-substituted aryl group, or an alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, Z1 to Z4 are the same as or different from each other and are each independently SR, and R is an alkyl group substituted with an alkyl-substituted heterocyclic group, an alkyl group substituted with an alkyl-substituted aryl group, or an alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present specification, Z1 to Z4 are the same as or different from each other and are each independently SR, and R is an alkyl group substituted with a heterocyclic group substituted with an alkyl group having 1 to 15 carbon atoms, an alkyl group substituted with an aryl group substituted with an alkyl group having 1 to 15 carbon atoms, or an alkyl group having 1 to 15 carbon atoms.

in particular, when the structure of S — R is introduced into Z1 to Z4, intermolecular aggregation can be induced by a strong interaction between S, which brings about an advantage of accelerating charge carrier transfer between molecules.

In one embodiment of the present specification, chemical formula 1 may be represented by any one of the following compounds.

in one embodiment of the present application, the first electrode and the second electrode are not particularly limited as long as they are known in the art. In one embodiment, the first electrode and the second electrode may each independently include indium-doped tin oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), indium-doped zinc oxide (IZO), ZnO, platinum, and the like, but are not limited thereto.

In one embodiment of the present application, the first electrode and the second electrode may each be a transparent electrode. Specifically, ITO having a transmittance of 80% or more may be used.

In one embodiment of the present application, the thickness of the first electrode and the second electrode are each independently 10nm to 500 nm.

The first electrode or the second electrode may mean a substrate coated with an anode active material generally used for an electrochromic device. In addition, one example of the substrate may be a current collector. Depending on the voltage range, a copper, nickel, or SUS collector may be used, and specifically, a copper collector may be used.

the anode may mean a material coated with a commonly used anode active material for an electrochromic device, and as its type, lithium, a metal material capable of forming an alloy with lithium, a transition metal oxide, a material capable of doping or dedoping lithium, a material capable of reversibly intercalating or deintercalating lithium ions, or the like may be used.

More specifically, according to one embodiment of the present application, the first electrode and the second electrode each independently comprise one or more types of metals selected from the group consisting of: lithium (Li), potassium (K), calcium (Ca), sodium (Na), magnesium (Mg), aluminum (Al), zinc (Zn), iron (Fe), nickel (Ni), tin (Sn), lead (Pb), copper (Cu), indium (In), titanium (Ti), vanadium (V), and zirconium (Zr), or an alloy thereof.

In addition, specific examples of the transition metal oxide may include vanadium oxide, lithium vanadium oxide, and the like, and examples of the material capable of doping and dedoping lithium may include Si, SiO, and the like_x(0<x<2) Si-Y alloy (Y is alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth element or combination thereof, but not Si), Sn, SnO₂Sn-Y (Y is an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a transition metal, a rare earth element, or a combination thereof, but not Sn), or the like, or at least one of them and SiO₂a mixture of (a).

Specific examples of the element Y are not particularly limited, but may include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po or combinations thereof.

The material capable of reversibly intercalating or deintercalating lithium ions is a carbon material, and any carbon-based anode active material generally used for an electrochromic device may be used, and as a typical example, crystalline carbon, amorphous carbon, or a combination thereof may be used. Examples of the crystalline carbon may include graphite in an amorphous form, a plate form, a flake form, a spherical form, or a fiber form such as natural graphite or artificial graphite, and examples of the amorphous carbon may include soft carbon (low-temperature-calcined carbon), hard carbon, mesophase pitch carbide, calcined coke, and the like.

one embodiment of the present application provides a method for manufacturing an electrochromic device, in which a method of forming an electrochromic layer is a solution method, such as spin coating.

in one embodiment of the present application, a method of forming the electrochromic layer is not particularly limited, and a method known in the art may be used. For example, a plating method, sputtering, an electron beam evaporation method, a chemical vapor deposition method, a sol-gel coating method, or the like can be used.

In one embodiment of the present application, the electrolyte layer may be prepared using materials and methods known in the art. Specifically, pentaerythritol triacrylate (PETA) monomer, 1M or greater LiClO may be used₄Polycarbonate, etc., however, the materials and methods are not limited thereto.

In one embodiment of the present application, a solid electrolyte or a liquid electrolyte may be used as the electrolyte layer, and the electrolyte layer is not particularly limited as long as it can exert an effect of transferring ions and electrons.

In one embodiment of the present application, the electrolyte layer may include lithium salts, plasticizers, oligomers, monomers, additives, radical initiators, and the like. The oligomers used in the present disclosure need to be compatible with the plasticizer.

The degree of discoloration and coloring can be adjusted by changing the thickness of the electrochromic layer, and the layer can be adjusted to be thin when transmittance is desired, and thick when opacity is desired rather than transparency.

In one embodiment of the present application, the thickness of the electrochromic layer may be greater than or equal to 10nm and less than or equal to 1.5 μm, preferably greater than or equal to 20nm and less than or equal to 1 μm.

One embodiment of the present application provides a method for manufacturing an electrochromic device, comprising: preparing a substrate; forming a first electrode on a substrate; forming a second electrode opposite to the first electrode; forming an electrolyte layer between the first electrode and the second electrode; and forming an electrochromic layer between the electrolyte layer and the second electrode, wherein one or more layers of the electrochromic layer include the compound for electrochromic according to chemical formula 1.

In the method for manufacturing an electrochromic device, the description of the compound for electrochromic used is the same as that of the compound for electrochromic in the electrochromic device.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

In the present application, a method for preparing a compound for electrochromism and a method for manufacturing an electrochromic device including the compound for electrochromism will be specifically described in the following preparation examples and examples. However, the following examples are for illustrative purposes only, and the scope of the present specification is not limited thereto.

Preparation example 1 preparation of Compound 1

(1) preparation of Compound A-2

1.49mL of phosphorus oxychloride (POCl)₃) (16mmol) was added to 1.55mL of N, N-Dimethylformamide (DMF) (20mmol), and the resultant was stirred at 0 ℃ for 60 minutes to prepare a mixture solution. To the prepared mixture solution was added a solution of compound A-1(1.53mmol) dissolved in 20mL of Dichloroethane (DCE), and the resultant was stirred at 100 ℃ for 48 hours. After stirring, 1M sodium hydroxide (NaOH) was added thereto, and the resultant was stirred for 1 hour to perform neutralization. Thereafter, the resultant was extracted with methylene chloride, and the extract was extracted with anhydrous magnesium sulfate (anhydrous MgSO)₄) Dried and evaporated. The solvent was removed under vacuum, and the residue was purified by flash chromatography using hexane and chloroform as eluents (hexane: chloroform ═ 4:1) to obtain 1.066g of compound a-2. (yield: 67.3%)

FIG. 2 is a graph showing the MS spectrum of Compound A-2.

(2) Preparation of Compound 1

Under nitrogen (N)₂) Under atmosphere, 2mL of pyridine was added to compound A-2(0.725g, 0.7mmol) and compound C-1(0.6 mmol)8g, 3.5mmol) was mixed in 40mL chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, acetone, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 905mg of compound 1. (yield: 93%)

Fig. 3 is a graph showing the MS spectrum of compound 1.

Preparation example 2 preparation of Compound 2

(1) Preparation of Compound B-2

To Tetrahydrofuran (THF) (100mL) in which compound B-1(2.5g, 9.4mmol) was dissolved was added sodium tert-butoxide (NaOC (CH)₃)₃) (4.13g, 43mmol) then a total of 2.58mL of carbon disulfide (CS) was added over 1 hour₂) (43 mmol). Thereafter, 2-ethylhexyl bromide (8.89mL, 50mmol) was added thereto, and the resultant was stirred for 24 hours. After the reaction, ammonium hydroxide (NH) was added thereto₄OH) to stop the reaction, the resultant was extracted with Dichloromethane (DCM) and then washed 3 times with water. The product was purified by chromatography using a silica gel column using hexane as an eluent to obtain 3.63g of compound B-2 as a red oil. (yield: 45%)

FIG. 4 is a graph showing the MS spectrum of Compound B-2.

(2) Preparation of Compound B-3

4mL of phosphorus oxychloride (POCl)₃) (43mmol) was added to N, N-Dimethylformamide (DMF) (55mmol), and the resultant was stirred at 0 ℃ for 60 minutes to prepare a mixtureAnd (3) solution. To the prepared mixture solution was added a solution of compound B-2(4.19mmol) dissolved in 40mL of Dichloroethane (DCE), and the resultant was stirred at 100 ℃ for 48 hours. After stirring, 1M sodium hydroxide (NaOH) was added thereto, and the resultant was stirred for 1 hour to perform neutralization. Thereafter, the resultant was extracted with methylene chloride, and the extract was extracted with anhydrous magnesium sulfate (anhydrous MgSO)₄) Dried and evaporated. The solvent was removed under vacuum, and the residue was purified by flash chromatography using hexane and chloroform as eluents (hexane: chloroform ═ 4:1) to obtain 2.47g of compound B-3. (yield: 64%)

FIG. 5 is a graph showing the MS spectrum of Compound B-3.

(3) Preparation of Compound 2

under nitrogen (N)₂) Under the atmosphere, 2mL of pyridine was added to a mixture of Compound B-3(0.44g, 0.48mmol) and Compound C-1(0.93g, 4.8mmol) in 30mL of chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 550mg of compound 2. (yield: 90%)

Fig. 6 is a graph showing the MS spectrum of compound 2.

PREPARATION EXAMPLE 3 preparation of Compound 3

under nitrogen (N)₂) Under atmosphere, three drops of piperidine were added to a mixture of Compound B-3(0.83g, 0.9mmol) and Compound C-2(1.45g, 9mmol) in 15mL of chloroform (CHCl)₃) Solution of (1)In the liquid. After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 918mg of compound 3. (yield: 84.3%) (MALDI-TOF MS:1208.3g/mol)

fig. 7 is a graph showing the UV spectrum of compound 3.

In fig. 7, (a) shows UV data of compound 3 in a solution state, (b) shows UV data of compound 3 measured in a film state, and (c) shows UV data of compound 3 measured after heat treatment at 110 ℃ for 10 minutes in a film state.

Here, the solution state is a state in which the compound 3 is dissolved in a chlorobenzene solution, and a film is formed by spin-coating the compound 3 in the solution state.

It is determined in fig. 7 that the electron vibration peak of (c) after the heat treatment of the film is increased compared to the electron vibration peak before the heat treatment of the film. Therefore, it was confirmed that the crystallinity after the heat treatment was superior.

Fig. 8 is a graph showing the results of measuring CV of compound 3.

Fig. 9 is a graph showing the MS spectrum of compound 3.

preparation example 4 preparation of Compound 4

(1) Preparation of Compound B-4

To a solution of compound B-1(1.25g, 4.7mmol) dissolved in Tetrahydrofuran (THF) (100mL) was added sodium tert-butoxide (NaOC (CH)₃)₃) (2.1g, 21.85mmol), the resultant was reacted for 1 hour, and then 1.31mL of carbon disulfide (CS) was added thereto₂) (21.85 mmol). Thereafter, the resultant was reacted for 1 hour and then added theretocompound C-3(6.53g, 25mmol) and the resulting mass was stirred for 24 hours. After the reaction, ammonium hydroxide (NH) was added thereto₄OH) to stop the reaction, the resultant was extracted with Dichloromethane (DCM) and then washed 3 times with water. The product was purified by chromatography using a silica gel column using hexane as an eluent to obtain 2.15g of compound B-4 as a red viscous oil. (yield: 40%) (LCQ MS:1140.1g/mol)

(2) preparation of Compound B-5

4mL of phosphorus oxychloride (POCl)₃) (43mmol) was added to N, N-Dimethylformamide (DMF) (55mmol), and the resultant was stirred at 0 ℃ for 60 minutes to prepare a mixture solution. To the prepared mixture solution was added a solution of compound B-4(4.77g, 4.19mmol) dissolved in 40mL of Dichloroethane (DCE), and the resultant was stirred at 100 ℃ for 48 hours. After stirring, 1M sodium hydroxide (NaOH) was added thereto, and the resultant was stirred for 1 hour to perform neutralization. Thereafter, the resultant was extracted with methylene chloride, and the extract was extracted with anhydrous magnesium sulfate (anhydrous MgSO)₄) Dried and evaporated. The solvent was removed under vacuum, and the residue was purified by flash chromatography using hexane and chloroform as eluents (hexane: chloroform ═ 4:1) to obtain 4.1g of compound B-5. (yield: 82%) (MALDI-TOF MS:1196.2g/mol)

(3) preparation of Compound 4

Under nitrogen (N)₂) Under the atmosphere, 2mL of pyridine was added to a mixture of Compound B-5(1g, 0.84mmol) and Compound C-1(1.55g, 8mmol) in 30mL of chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 950mg of compound 4. (yield: 73%) (MALDI-TOF MS:1548.2g/mol)

preparation example 5 preparation of Compound 5

Under nitrogen (N)₂) Under atmosphere, three drops of piperidine were added to a mixture of Compound B-5(1g, 0.84mmol) and Compound C-4(1.96g, 8mmol) in 30mL of chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 1.04g of compound 5. (yield: 75%) (MALDI-TOF MS:1650.6g/mol)

PREPARATION EXAMPLE 6 preparation of Compound 6

(1) Preparation of Compound B-6

To a solution of compound B-1(1.25g, 4.7mmol) dissolved in Tetrahydrofuran (THF) (100mL) was added sodium tert-butoxide (NaOC (CH)₃)₃) (2.1g, 21.85mmol) and then the resultant was reacted for 1 hour. After the reaction, 1.31mL of carbon disulfide (CS) was added thereto₂) (21.85mmol), and the resultant was reacted for 1 hour. Thereafter, Compound C-5(6.38g, 25mmol) was added thereto, and the resultant was stirred for 24 hours. After the reaction, ammonium hydroxide (NH) was added thereto₄OH) to stop the reaction, the resulting material was extracted with Dichloromethane (DCM), then washed 3 times with water. The product was purified by chromatography using a silica gel column using hexane as an eluent to obtain 2.5g of compound B-6 as a red viscous oil. (yield: 48%) (LCQ MS:1115.3g/mol)

(2) Preparation of Compound B-7

4mL of phosphorus oxychloride (POCl)₃) (43mmol) was added to N, N-Dimethylformamide (DMF) (55mmol), and the resultant was stirred at 0 ℃ for 60 minutes to prepare a mixture solution. To the prepared mixture solution was added a solution of compound B-6(4.67g, 4.19mmol) dissolved in 40mL of Dichloroethane (DCE), and the resultant was stirred at 100 ℃ for 48 hours. After stirring, 1M sodium hydroxide (NaOH) was added thereto, and the resultant was stirred for 1 hour to perform neutralization. Thereafter, the resultant was extracted with methylene chloride, and the extract was extracted with anhydrous magnesium sulfate (anhydrous MgSO)₄) Dried and evaporated. The solvent was removed under vacuum, and the residue was purified by flash chromatography using hexane and chloroform as eluents (hexane: chloroform ═ 4:1) to obtain 3.5g of compound B-7. (yield: 71%) (MALDI-TOF MS:1171.2g/mol)

(3) Preparation of Compound 6

Under nitrogen (N)₂) Under atmosphere, three drops of piperidine were added to a mixture of Compound B-7(1g, 0.85mmol) and Compound C-2(1.29g, 8mmol) in 30mL of chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 970mg of compound 6. (yield: 78%) (MALDI-TOF MS:1457.6g/mol)

PREPARATION EXAMPLE 7 preparation of Compound 7

under nitrogen (N)₂) Under the atmosphere, 2mL of pyridine was added to a mixture of Compound B-7(1g, 0.85mmol) and Compound C-1(1.55g, 8mmol) in 30mL of chloroform (CHCl)₃) In the solution of (1). After refluxing the mixture solution under nitrogen atmosphere for 24 hours, the solution was taken up in dichloromethane (CH)₂Cl₂) Extracted and washed with water. After removing the solvent, the resultant was recrystallized through Methyl Chloride (MC)/methanol, and hexane, ethyl acetate and chloroform (CHCl) were used₃) The product was purified by chromatography using silica gel column as eluent. The resulting solid was recrystallized from chloroform. Thereafter, the resultant was washed with methanol and dried under vacuum to obtain 910mg of compound 7. (yield: 70%) (MALDI-TOF MS:1524.1g/mol)