KR101742782B1 - New triazolothiadiazole compound, uses thereof, and organic electroluminescent devices having the same - Google Patents

New triazolothiadiazole compound, uses thereof, and organic electroluminescent devices having the same Download PDF

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KR101742782B1
KR101742782B1 KR1020150094907A KR20150094907A KR101742782B1 KR 101742782 B1 KR101742782 B1 KR 101742782B1 KR 1020150094907 A KR1020150094907 A KR 1020150094907A KR 20150094907 A KR20150094907 A KR 20150094907A KR 101742782 B1 KR101742782 B1 KR 101742782B1
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이기환
살림 무하마드
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공주대학교 산학협력단
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Abstract

The present invention relates to a triazolo thiadiazole compound represented by the following formula (1), wherein R is a substituted or unsubstituted polycyclic aryl group or metallocenyl group having 10 to 25 carbon atoms.
The novel triazolothiadiazole compound containing R of the present invention has excellent luminescence characteristics and thermal stability having a wide wavelength range from red to blue, and thus has an excellent light-emitting property and thermal stability in an organic electronic device such as a light emitting device or a dye- Can be used effectively.
[Chemical Formula 1]

Figure 112015064575759-pat00023

Description

TECHNICAL FIELD [0001] The present invention relates to a novel triazolo thiadiazole compound, its use, and an organic light emitting device including the same. BACKGROUND ART [0002]

The present invention relates to a novel triazolothiadiazole compound, its use, and an organic light emitting device containing the same.

2. Description of the Related Art In recent years, the importance of a flat panel display (FPD) has been increasing with the development of multimedia. In response to this, various kinds of devices such as a liquid crystal display (LCD), a plasma display panel (PDP), a field emission display (FED), an organic light emitting diode Branch displays have been put into practical use.

Among these organic electroluminescent devices, devices can be formed on a flexible substrate such as a plastic substrate. Further, the organic electroluminescent device can be driven at a voltage as low as 10 V or less as compared with a plasma display panel or an inorganic electroluminescent display, It has the advantage of being excellent. In addition, organic light emitting devices can display three colors of red, green, and blue, which is a next-generation display device that expresses rich colors, and has become a target of many people.

One of the biggest problems in the organic electronic device is the compatibility with the light emitting efficiency, color purity and durability of the device. Particularly, in an organic light emitting device, a luminescent dye (dopant) may be added to the luminescent layer (host) to increase the efficiency and stability of the luminescent state.

In such a structure, the efficiency and performance of the light emitting device are changed depending on which host material is used for the light emitting layer. As an example of a material used for the light emitting layer (host) of the organic light emitting device, Japanese Patent Application Laid- Or an anthracene substituted with two naphthyl groups as a compound which can be used for the hole injection layer. However, the compound is insufficient in solvent solubility, and the luminescent characteristics and thermal stability of the organic light emitting device employing the compound are not satisfactory.

Therefore, it is still required to develop a material having excellent thermal stability and long life, and having excellent luminescence properties.

On the other hand, since the fused heterocyclic compound not only has an easy synthesis method and excellent variable optical properties but also is biomolecular-friendly, it can be applied to organic light emitting diodes, luminescent materials, dye-sensitized solar cells, bioimaging, It is getting big attention.

In particular, as examples of fused heterocyclic compounds, triazolothiadiazole compounds have attracted considerable interest due to their ease of synthesis and potential pharmaceutical applications.

The triazolo thiadiazole compounds derived from the prior art are 1,2,4-triazolo [3,4-b] [1,3,4] thiadiazole (1,2,4-triazolo [3,4 -b] [1,3,4] thiadiazole (Non-Patent Document 1 and Non-Patent Document 2), 3- (phenyl) -6- (4-aminophenyl) [1,2,4] triazolo [ 4-b] [1,3,4] thiadiazole (3- (phenyl) -6- (4-aminophenyl) thiadiazole (Non-Patent Document 3). The triazolothiadiazole compound is different from the triazolothiadiazole compound of the present invention in the kind and position of the substituent, and is also useful as a pharmaceutical material for antibacterial and immunological purposes An enzyme inhibitor, and the like, and there are no examples that are used as a light emitting material.

[Non-Patent Document 1]: Mahadev B.T. Shoba R.D. Yallappa S.S. Subash C. M., Shankar C. B., Ind. J. of hetro. Chem., 1996, 5, 215-218. [Non-patent Document 2]: Silver stenin R.M. Bassler, Morrd T. C., spectrometric identification of organic compounds, 1979, 5, 328. [Non-Patent Document 3]: Kokila Parmar, Sarju Prajapati, Rinku Patel, Sejal Joshi, Rekha Patel; International Journal of ChemTech Research CODEN (USA), IJCRGG ISSN, 0974-4290 Vol. 3, No.2, pp 761-765, April-June 2011

The inventors of the present invention have investigated fluorescence or luminescent materials in which a triazole thiadiazole compound containing R group (R is selected from the group consisting of substituted or unsubstituted polycyclic aryl group having 10 to 25 carbon atoms and a metallocenyl group ) Is excellent in thermal stability and luminescence characteristics and can be used for an organic electronic device.

Accordingly, it is an object of the present invention to provide a triazolothiadiazole compound containing the R group, a fluorescent or luminescent composition containing the same, a method for producing the same, and an organic electronic device including the same.

According to one aspect of the present invention, there is provided a triazolothiadiazole compound represented by the following formula (1).

[Chemical Formula 1]

Figure 112015064575759-pat00001

Wherein R is any one selected from the group consisting of a substituted or unsubstituted polycyclic aryl group and a metallocenyl group having 10 to 25 carbon atoms.

In one embodiment, R is selected from the group consisting of biphenyl, naphthyl, p-terpheny, pyrenyl, and ferrocenyi And the triazolothiadiazole compound may be any one selected from the group consisting of

[1] 6 - [(1,1'-biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] 3,4] thiadiazole (6 - [(1,1'-Biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [ , 3,4] thiadiazole),

[2] Synthesis of 3- (4-methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole 3- (4-Methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole)

[3] Preparation of 6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [ 4-b] [1,3,4] thiadiazole (6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) 2,4] triazolo [3,4-b] [1,3,4] thiadiazole),

[4] 3- (4-methoxybenzyl) -6- (pyrene-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole (3- (4-Methoxybenzyl) -6- (pyren-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole, and

[5] Preparation of 6- (4-ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole - (4-Ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole)

. ≪ / RTI >

According to one aspect of the present invention, there is provided a fluorescent or luminescent composition comprising the compound.

According to one aspect of the present invention, there is provided a process for producing a carboxylic acid (R-COOH) (R is a substituted or unsubstituted monocyclic aryl group and a metallocenyl group having 10 to 25 carbon atoms) Wherein R 1 and R 2 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an alkoxy group, an alkoxy group, and an alkoxy group.

[Chemical Formula 1]

Figure 112015064575759-pat00002

Wherein R is any one selected from the group consisting of a substituted or unsubstituted polycyclic aryl group and a metallocenyl group having 10 to 25 carbon atoms.

[Formula 1e]

Figure 112015064575759-pat00003
.

In one embodiment, the carboxylic acid containing R groups is selected from the group consisting of biphenylcarboxylic acid, naphthylcarboxylic acid, p-terphenylcarboxylic acid, pyrenylcarboxylic acid and ferrocenylcarboxylic acid It can be either.

In one embodiment, the compound of formula (1e) is prepared by a) reacting a compound of formula (1a) with phosphorus oxychloride to form a compound of formula (1b) b) reacting a compound of formula 1b with hydrazine hydrate to form a compound of formula 1c; c) reacting a compound represented by the following formula (1c) with a carbon disulfide to form a compound represented by the following formula (1d); And d) reacting a compound represented by the following formula (1d) with hydrazine hydrate to form a compound represented by the following formula (1e).

[Formula 1a]

Figure 112015064575759-pat00004
,

[Chemical Formula 1b]

Figure 112015064575759-pat00005
,

[Chemical Formula 1c]

Figure 112015064575759-pat00006
,

≪ RTI ID = 0.0 &

Figure 112015064575759-pat00007
.

According to one aspect of the present invention, there is provided an organic electronic device comprising the triazolothiadiazole compound.

In one embodiment, the organic electronic device may be an organic light emitting diode (OLED) or a dye-sensitized solar cell (DSSC).

In one embodiment, the structure of the organic light emitting device OLED includes an anode; A hole injection layer (HIL) formed on the anode; A hole transport layer (HTL) formed on the hole injection layer; An emission layer (EML) formed on the hole transport layer and including a fluorescent dopant including the triazole thiadiazole compound; An electron transport layer (ETL) formed on the light emitting layer; And a cathode formed on the electron transport layer.

According to the present invention, it has been found that a novel triazolo thiadiazole compound having an R group that extends the conjugation length has excellent light emission characteristics and thermal stability having a wide wavelength range from red to blue.

Accordingly, the novel triazolo thiadiazole compound according to the present invention has a long life span, excellent durability, excellent color purity and efficiency, and is useful as an organic light emitting device or dye-sensitized solar cell organic electronic device, Lt; / RTI >

Fig. 1 is a graph showing the results of evaluating the fluorescence quantum yield of the compound [1].
2 is a graph showing the results of evaluating the fluorescence quantum yield of the compound [2].
3 is a graph showing the results of the evaluation of the fluorescence quantum yield of the compound [3].
4 is a graph showing the results of evaluating the fluorescence quantum yield of the compound [4].
5 is a graph showing the results of evaluating the fluorescence quantum yield of the compound [5].
6A to 6E are pyrolysis analysis (TGA) graphs showing the results of evaluation of the thermal stability of the compounds [1] to [5], respectively.
7 shows the boundary molecular orbital functions HOMO and LUMO of the compounds [1] to [5] according to the present invention.
8 is a schematic view of a cross-sectional structure of an organic light emitting diode (OLED) according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides a novel triazolothiadiazole compound represented by the following formula (1).

[Chemical Formula 1]

Figure 112015064575759-pat00008

In Formula 1, R is any one selected from the group consisting of a substituted or unsubstituted polycyclic aryl group and a metallocenyl group having 10 to 25 carbon atoms, and examples thereof include a biphenyl group, a naphthyl group, a terphenyl group, A perylene group, a perylene group, a perylene group, a perylene group, a perylene group, a perylene group, a perylene group, a perylene group,

Specific examples of the compound represented by the formula (1) are as follows:

[1] 6 - [(1,1'-biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] 3,4] thiadiazole (6 - [(1,1'-Biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [ , 3,4] thiadiazole),

[2] Synthesis of 3- (4-methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole 3- (4-Methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole)

[3] Preparation of 6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [ 4-b] [1,3,4] thiadiazole (6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) - [ 2,4] triazolo [3,4-b] [1,3,4] thiadiazole),

[4] 3- (4-methoxybenzyl) -6- (pyrene-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole (3- (4-Methoxybenzyl) -6- (pyren-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole, and

[5] Preparation of 6- (4-ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole - (4-Ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4-b] [1,3,4] thiadiazole.

The triazolothiadiazole compound according to the present invention exhibits a broad wavelength shift, can easily be changed from blue to red, exhibits high thermal stability, and exhibits an excellent effect as an organic material for a light emitting layer.

Further, the present invention provides a triazolothiadiazole composition for fluorescence or luminescence represented by the above-mentioned formula (1).

The present invention also provides a process for preparing a triazolothiadiazole compound represented by the general formula (1).

A method for producing a triazolothiadiazole compound represented by the formula (1) according to the present invention comprises reacting a compound represented by the formula (1e) with a carboxylic acid (R-COOH) containing an R group wherein R is a substituted or unsubstituted A polycyclic aryl group, and a metalloceneyl group) to form a compound represented by the formula (1), and may further include other processes as necessary.

Figure 112015064575759-pat00009

Here, the compound represented by Formula 1e can be prepared by a known method.

The R group-containing carboxylic acid may be any one selected from the group consisting of biphenylcarboxylic acid, naphthylcarboxylic acid, p-terphenylcarboxylic acid, pyrenylcarboxylic acid and ferrocenylcarboxylic acid. But is not limited thereto.

(A) reacting a compound represented by the following formula (1a) with phosphorus oxychloride to form a compound represented by the following formula (1b); and reacting the compound represented by the formula b) reacting a compound represented by the following formula (1b) with hydrazine hydrate to form a compound represented by the following formula (1c); c) reacting a compound represented by the formula (1c) with a carbon disulfide to obtain a compound represented by the formula ; And d) reacting the compound represented by the formula (1d) with hydrazine hydrate to form a compound represented by the following formula (1e).

[Reaction Scheme 1]

Figure 112015064575759-pat00010

Hereinafter, a method of preparing the compound represented by Formula 1e will be described in detail.

The step a) of the present invention is a step of reacting a compound represented by the following formula (1a) with phosphorus oxychloride to form a compound represented by the following formula (1b), more specifically, a compound represented by the formula Next, the reaction is carried out under refluxing with phosphorus oxychloride to prepare the intermediate product, the compound represented by the formula (1b).

Figure 112015064575759-pat00011

At this time, since the compound represented by Formula 1b formed in the above step exists in a solvent as described above, the solvent containing the compound is cooled to room temperature and then removed under reduced pressure to obtain the compound represented by Formula 1b.

Also, it is preferable to use at least one solvent which is inert to the reactants, for example, a chlorinated aliphatic solvent such as dichloromethane or 1,2-dichloroethane, more preferably 1, 2- But is not limited to, dichloroethane as a solvent.

Next, the step b) of the present invention is a step of reacting the compound represented by the formula 1b prepared in the step a) with hydrazine hydrate to form a compound represented by the formula 1c, more specifically, a compound represented by the formula 1b and hydrazine Hydrate may be added dropwise to a nitrogen-containing solution containing hydrazine hydrate to form a compound represented by the formula (1c).

Figure 112015064575759-pat00012

At this time, the nitrogen-containing solvent may be, but not limited to, acetonitrile, triethanolamine or a mixed solvent thereof.

Next, the step c) of the present invention is a step of reacting a compound represented by the following formula 1c with a carbon disulfide to form a compound represented by the following formula 1d. More specifically, the potassium hydroxide is dissolved in dry methanol , Followed by addition of the compound represented by the formula 1c prepared in the above step b), followed by cooling on ice. Subsequently, the carbon disulfide is added in small amounts while continuously stirring in the same amount as the compound represented by the above formula (1c) for 1 to 5 hours, more preferably for 2 to 3 hours.

Figure 112015064575759-pat00013

The compound represented by the formula (1d) thus formed can be obtained by filtration, followed by washing with a cold organic solvent (for example, diethyl ether) and drying.

Next, the step d) according to the present invention is a step of reacting a compound represented by the following formula (1d) with hydrazine hydrate to form a compound represented by the following formula (1e), more specifically, a compound represented by the formula The deionized water is treated without purification of the compound, then hydrazine hydrate is added and refluxed.

Figure 112015064575759-pat00014

As a result, the reaction mixture turns into yellowish green with the generation of hydride sulfide, and finally it is homogenized. Thus, by crushing crushed ice and acidifying it by adding an acid, finally a compound represented by the formula (1e) can be obtained.

Therefore, the method of the present invention for producing triazolothiadiazole compounds can be carried out by a very simple method in which a high yield of a triazolothiadiazole compound is obtained without involving a complicated chromatographic technique performed to obtain a pure compound as in the conventional method Can be obtained.

Further, the present invention provides an organic electronic device comprising the triazolothiadiazole compound represented by the above formula (1).

The organic electronic device of the present invention may be, for example, an organic light emitting diode (OLED) or a dye-sensitized solar cell (DSSC).

In one embodiment, the structure of the organic light emitting device comprises, for example, an anode; A hole injection layer (HIL) formed on the anode; A hole transport layer (HTL) formed on the hole injection layer; An emission layer (EML) formed on the hole transport layer and including a fluorescent dopant including the triazole thiadiazole compound; An electron transport layer (ETL) formed on the light emitting layer; And a cathode formed on the electron transport layer, and the structure thereof is shown in FIG.

Specifically, the anode is connected to one of a source electrode and a drain electrode of the thin film transistor to receive a driving current applied from the thin film transistor. The anode may be made of a known electrode material used for an organic light emitting device And may be a transparent metal oxide electrode such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or the like.

The hole injection layer formed on the anode moves the holes injected from the anode in a direction in which the light emitting layer is positioned and assists injection of holes.

Such a hole injecting layer may include a hole injecting material and a metal oxide or organic p-type dopant.

The metal oxide may be an oxide containing a transition metal. Examples of the transition metal include molybdenum, tungsten, vanadium, rhenium, ruthenium, chromium, manganese, nickel, iridium, APC (silver-palladium-copper alloy), combinations thereof, and the like. Examples of the organic p-type dopant include tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) or tris [1,2-bis (trifluoromethyl) ethane-1,2-dithiolene [Mo (tfd) 3 ] and the like.

Meanwhile, the hole injection layer preferably has a thickness of 1 to 100 nm in order to achieve an improved efficiency, prevent an excessive increase in driving voltage, and achieve color coordinates close to NTSC (National Television System Committee) color coordinates.

Next, a hole transporting layer for transporting the holes injected from the anode to the light emitting layer is provided on the hole injecting layer. The hole transporting layer material may be a known material for the hole transporting layer, and the 4,4'-bis [ N-phenylamino] biphenyl (NPB), 4,4'-bis [N- (3-methylphenyl) Bis (4- (N, N-di-p-tolylamino) phenyl) cyclohexane (TAPC), 4 "-tris [(3- methylphenyl) phenylamino] triphenylamine (MTDATA) (TCTA), 9,9 '- [1,1', 8-tetramethyl-4- (9H-carbazol-9- (Biphenyl) -4,4'-diylbis-9H-carbazole (CBP), 9,9 ' , 2 '' - (1,3,5-benzenetriyl) tris- [1-phenyl-1H-benzimidazole] (TPBi), and the like.

Meanwhile, it is preferable that the hole transport layer has a thickness of 1 to 100 nm in order to achieve an improved efficiency, prevent an excessive increase of the driving voltage, and realize color coordinates close to NTSC (National Television System Committee) color coordinates.

A light emitting layer is provided on the hole transporting layer. The light emitting layer is injected from the cathode and injected from the anode through the electron transport layer and recombined with the holes passing through the hole transport layer to generate an exciton and the generated exciton exiting from the excited state changes to the base state Layer may be composed of a single layer or a multi-layer.

The light emitting layer includes a host for charge transport and a fluorescent dopant. For example, 1,3-N, N-dicarbazole benzene (mCP) and compounds thereof are preferably used as the host, but not limited thereto, and 4,4'-N, N- Dicarbazolebiphenyl (CBP), (4,4'-bis (2,2-diphenyl-ethen-1-yl) diphenyl (DPVBi), bis (styryl) amine (DSA) Aluminum (III) (BAlq), bis (2-methyl-8-quinolinolato) (triphenylsiloxy) aluminum 4- (4-ethylphenyl) -1,2,4-triazole (p-EtTAZ), 3- (4-biphenyl) (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,2 ', 7,7'-tetrakis -9,9'-spirofluorene (Spiro-DPVBI), tris (para-phenyl-4-yl) amine (p-TTA), 5,5- Bithiophene (BMB-2T), perylene, and the like may also be used.

Herein, as the fluorescent dopant, a luminescent layer having excellent luminescence properties and thermal stability can be formed by using the triazolothiadiazole oil of the formula (1) according to the present invention.

In the present invention, the electron transporting layer may include an electron transporting layer having a thickness of 5.0 x 10 < -6 > cm < 2 > / Vs or less and an electron transporting layer (4-biphenyl) -4- (phenyl-5-tert-butylphenyl-1,2,4-triazole) is preferably used as the material of the electron mobility. (3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole: TAZ).

A negative electrode is provided on the electron transporting layer. The cathodes are commonly connected to the power supply voltage and inject electrons into the electron transport layer. The cathode may be formed of a metal having a low work function as a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, have. It may also be formed of a multilayer structure material such as LiF / Al or LiO 2 / Al.

Electroluminescent devices using organic materials can overcome the limitations of inorganic materials due to low driving voltage, various colors ranging from blue to red, fast response speed, and especially excellent processability.

The triazolothiadiazole compound according to the present invention exhibits a broad wavelength shift and can be easily converted from blue to red, and can exhibit an excellent effect as an organic material forming a light emitting layer.

In addition, the synthesized triazolothiadiazole compound exhibits a significantly high thermal stability and can be effectively applied to an organic light emitting diode (OLED) or a dye-sensitized solar cell (DSSC).

Therefore, by using the compound (triazolothiadiazole compound) according to the present invention, it is possible to realize an organic electronic device (particularly, an organic light emitting device (OLED)) having a long lifetime, excellent durability and excellent color purity and efficiency.

Hereinafter, the present invention will be described in more detail through examples and test examples. However, the following examples and test examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

1. Substrate and reagent

A biphenyl carboxylic acid, a naphthyl carboxylic acid, a p-terphenyl carboxylic acid, a pyrenyl carboxylic acid, a ferrocenyl The ferrocenyl carboxylic acid And phosphorous oxychloride are available from Aldrich at 80% hydrazine hydrate, triethanolamine (TEA), carbon disulphide (CS 2 ), potassium hydroxide (KOH) and sodium bicarbonate (NaHCO 3 ) From Sigma-Aldrich, a mixture of ethanol, methanol, chloroform, water, acetonitrile, dimethyl sulfoxide, petroleum ether, ethyl acetate ( ethyl acetate), n-hexane was obtained from Samchun Chemicals (Korea), sulfuric acid (H 2 SO 4 ) and hydrochloric acid (HCl) from Jin Chemical & Pharmaceutical Co. Ltd., Korea, and used for the experiments.

Synthesis Example 1: Synthesis of 2- (4-methoxyphenyl) acetyl chloride (Compound 1b)

1 mmol of 2- (4-methoxyphenyl) acetic acid (Compound 1a) was refluxed for 3 hours in the presence of 12 mL of a 1,2-dichloroethane solvent and 0.4 mL of a chlorine-treating agent for phosphorous or oxychloride, 2- (4-methoxyphenyl) acetyl chloride (compound 1b) was synthesized.

The resulting solution was cooled to room temperature and the solvent was removed under reduced pressure to give compound 1b which was used directly in the next step without further purification.

Synthesis Example 2: Synthesis of 2- (4-methoxyphenyl) acetohydrazide (Compound 1c)

The compound 1b was dissolved in 80 mL of acetonitrile and added dropwise to a solution containing 1 mmol of hydrazine hydrate, 0.5 mL of TEA and 20 mL of acetonitrile, and this was subjected to thin layer chromatography (TLC) And refluxed for 3 hours.

The R f value of the TLC was calculated using an aluminum plate coated with silica gel (Kieselgel 60 F 254 , Merck (Germany)) and the developed TLC was confirmed using a UV lamp (VL-4 LC, France).

After all of the reactants were exhausted, the reaction mixture was cooled to room temperature. The solvent was then evaporated under reduced pressure to give 2- (4-methoxyphenyl) acetohydrazide (compound 1c) as a white solid which was purified by column chromatography and crystallized from methanol to give a white solid product Compound 1c) (86%).

IR spectra for the solid products were recorded using the KBr pellet method using a SHIMADZU FTIR-8400S spectrometer (Kyoto, Japan).

In addition, 1 H NMR & 13 C NMR spectrometers were recorded using a Bruker Avance 400 MHz spectrometer with TMS as the internal standard.

In addition, the chemical shift is a function of δ which is obtained from internal tetramethylsilane as an organic solvent (Ppm), and the singlet, doublet, and multiplet were expressed as 's', 'd' and 'm', respectively, depending on the characteristics of the peak.

Further, the following DMSO- d 6 means Dimethyl sulfoxide- d 6 , and the following FT-IR spectroscopy means Fourier transform infrared spectroscopy.

White solid; Yield: 86%; mp 134-136 [deg.] C; R f : 0.54 (n-hexane: ethyl acetate, 1: 1); FT-IR (υ / cm -1 ): 3334, 3302 (NH 2 ), 3205 (NH) 3037 (sp 2 CH), 2958, 2837 (sp 3 CH), 1610 1497 (C = C of phenyl ring); 1H NMR (400 M Hz, DMSO -d 6) 9.21 (s, 1H, NH), 7.19 (aromatic, d, 2H, J = 8.4 Hz), 6.86 (aromatic, d, 2H, J = 8.4 Hz), 4.23 (s, 2H, broad, NH 2), 3.71 (s, 3H, OCH 3), 3.28 (s, 2H, CH 2); 13C NMR (100 MHz, DMSO- d 6) 170.7, 159.6, 143.2, 129.7, 120.8, 114.6, 111.7, 55.3, 35.4.

Synthesis Example 3: Synthesis of 2- [2- (4-methoxyphenyl) acetyl] hydrazinecarbodithioate (Compound 1d)

0.125 mol of 2- (4-methoxyphenyl) acetohydrazide (compound 1c) was added to a solution of 0.125 mol of potassium hydroxide (KOH) in 50 mL of dry methanol, followed by cooling on ice. To this, 0.125 mol of carbon disulfide was added little by little while continuously stirring for 2 to 3 hours. The resulting solid substance, potassium-2- [2- (4-methoxyphenyl) acetyl] hydrazine carbodithioate (compound 1d), was filtered, washed with cold diethyl ether and dried . It was used immediately in the next step without purification.

Synthesis Example 4 Synthesis of 4-amino-3- (4-methoxybenzyl) -1H-1,2,4-triazole-5 (4H) -thione (Compound 1e)

2- (2- (4-methoxyphenyl) acetyl] hydrazine carbodithioate (compound 1d) was added to 20 mL of deionized water, and 0.250 mol of hydrazine hydrate was added thereto, followed by refluxing for 8-10 hours. The reaction mixture turned yellowish green with the generation of hydrozenesulfide, and finally homogenized. The mixture was then poured into crushed ice and acidified by the addition of hydrochloric acid (HCl).

The white precipitate of 4-amino-3- (4-methoxybenzyl) -1 hydrogen-1,2,4-triazole-5 (4H) -thione (compound 1e) thus formed was filtered, washed with cold water And crystallized with aqueous methanol to give a white solid material (Compound 1e) (75%).

White solid; Yield: 75%; mp 215-217 [deg.] C; Rf: 0.71 (pet ether: ethyl acetate, 7: 3); IR (v / cm -1 ) 3294, 3130 (NH), 3350-3273 (NH 2 ), 2937 (sp 2 CH), 1585 (C = N), 1561-1506 S); 1H NMR (400 MHz, CDCl 3 ) δ 13.81 (s, 1H, NH), 7.98-7.95 (m, 2H, Ar-H), 7.07-6.97 (m, 2H, Ar-H), 5.76 (s, 2H , NH 2), 3.72 (s , 3H, OCH 3); 13 C NMR (100 MHz, CDCl 3 )? 167.12, 161.31, 158.22, 132.57, 130.11, 118.61, 56.32

Example 1: Synthesis of 6 - [(1,1'-biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] , 3,4] thiadiazole (Compound [1])

1 mM of biphenylcarboxylic acid contained in 8 to 10 mL of phosphorus oxychloride and 1 mM of compound 1e were refluxed for 5 to 6 hours. The reaction mixture was slowly poured into crushed ice with stirring and neutralized with sodium bicarbonate (NaHCO 3 ). The resulting solid material (6 - [(1,1'-biphenyl) -4-yl] -3- (4- methoxybenzyl) - [1,2,4] triazolo [3,4- b] 1,3,4] thiadiazole) was filtered out, washed with cold water and dried to obtain a yellow solid (compound [1]) (77%).

Yellow solid; Yield: 77%; Rf : 0.43 (chloroform: methanol, 9: 1); IR (? / Cm -1 ): 3018 (sp 2 CH), 2930, 2854 (sp 3 CH), 1577 (C = N), 1544, 1521, 1496 (C = C), 1021 (Cs); 1H NMR (400 MHz, CDCl 3 ) δ 8.01-7.95 (m, 2H, Ar-H), 7.75-7.45 (m, 2H, Ar-H), 7.31-7.27 (m, 2H, Ar-H), 7.75 2H, Ar-H), 7.50-7.39 (m, 3H, Ar-H), 7.25-7.15 (m, 2H, Ar-H), 7.59-7.51 , 6.97-6.92 (m, 2H, Ar -H), 4.51 (s, 2H, CH 2), 3.89 (s, 3H, OCH 3); 13C NMR (100 MHz, CDCl 3 ) δ 163.3, 160.2, 159.4, 149.1, 133.4, 131.0, 128.5, 128.4, 126.4, 125.3, 122.4, 122.1, 122.0, 119.7, 118.7, 115.6, 114.5, 55.7, 28.9.

Example 2: Preparation of 3- (4-methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole (Compound [2])

1 mM of biphenylcarboxylic acid contained in 8 to 10 mL of phosphorus oxychloride and 1 mM of compound 1e were refluxed for 5 to 6 hours. The reaction mixture was poured slowly into crushed ice with stirring, which was then neutralized with sodium bicarbonate. The resulting solid material (3- (4-methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] The sol was filtered, washed with cold water and dried to obtain a yellowish white solid (compound [2]) (81%).

Yellowish white solid; Yield: 81%; Rf : 0.47 (chloroform: methanol, 9: 1); IR (? / Cm -1): 3021 (sp 2 CH), 2935, 2894 (sp 3 CH), 1588 (C = N), 1540, 1507, 1478 (C = C), 1017 (Cs); 1H NMR (400 MHz, CDCl 3 ) δ 8.00-7.91 (m, 1H, Ar-H), 7.86-7.81 (m, 2H, Ar-H), 7.76-7.74 (m, 1H, Ar-H), 7.67 (M, 2H, Ar-H), 7.27-7.18 (m, 2H, Ar-H), 7.56-7.47 , 4.49 (s, 2H, CH 2), 3.87 (s, 3H, OCH 3); 13 C NMR (100 MHz, CDCl 3 )? 163.7, 161.0, 158.9, 149.7, 134.2, 134.0, 130.1, 128.7, 127.1, 126.4, 123.8, 119.4, 118.9, 118.4, 115.7, 114.8, 114.5,

Example 3: Synthesis of 6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [3 , 4-b] [1,3,4] thiadiazole (Compound [3])

1 mM of biphenylcarboxylic acid contained in 8 to 10 mL of phosphorus oxychloride and 1 mM of compound 1e were refluxed for 5 to 6 hours. The reaction mixture was poured slowly into crushed ice with stirring and neutralized with sodium bicarbonate. The resulting solid material (6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4- methoxybenzyl) - [1,2,4] triazolo [ 3,4-b] [1,3,4] thiadiazole) was filtered off, washed with cold water and dried to give a septic color solid substance (compound [3]) (75%).

Seaweed solid; Yield: 75%; Rf : 0.48 (chloroform: methanol, 9: 1); IR (v / cm -1 ): 3037 (sp 2 CH), 2936, 2874 (sp 3 CH), 1578 (C = N), 1534, 1517, 1487 (C = C), 1024 (CS); 1H NMR (400 MHz, CDCl 3 ) δ 7.81-7.79 (m, 2H, Ar-H), 7.67-7.61 (m, 2H, Ar-H), 7.24-7.14 (m, 2H, Ar-H), 7.05 -6.64 (m, 11H, Ar- H), 4.51 (s, 2H, CH 2), 3.87 (s, 3H, OCH 3); 13C NMR (100 MHz, CDCl 3 ) δ 163.5, 161.1, 160.0, 149.4, 135.6, 134.1, 133.1, 130.4, 127.4, 127.3, 127.0, 125.6, 122.3, 121.8, 120.7, 118.7, 118.2, 115.6, 114.3, 55.6, 28.7.

Example 4: Preparation of 3- (4-methoxybenzyl) -6- (pyrene-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] Synthesis of sol (compound [4])

1 mM of biphenylcarboxylic acid contained in 8 to 10 mL of phosphorus oxychloride and 1 mM of compound 1e were refluxed for 5 to 6 hours. The reaction mixture was poured slowly into crushed ice with stirring, which was then neutralized with sodium bicarbonate. The resulting solid material (3- (4-methoxybenzyl) -6- (pyrene-4-yl) - [1,2,4] triazolo [3,4- b] Diazole) was filtered off, washed with cold water and dried to give a cream-colored solid (compound [4]) (77%).

Cream colored solid; Yield: 77%; Rf : 0.40 (chloroform: methanol, 9: 1); IR (? / Cm -1 ): 3022 (sp 2 CH), 2933, 2861 (sp 3 CH), 1578 (C = N), 1540, 1521, 1500 (C = C), 1023 (CS); 1H NMR (400 MHz, CDCl 3 ) δ 7.90-7.56 (m, 9H, Ar-H), 7.18-7.11 (m, 2H, Ar-H), 6.96-6.87 (m, 2H, Ar-H), 4.52 (s, 2H, CH 2) , 3.88 (s, 3H, OCH 3); 13 C NMR (100 MHz, CDCl 3 ) 隆 165.3, 164.0, 159.8, 149.4, 134.6, 133.2, 132.4, 130.4, 132.4, 130.2, 129.5, 127.3, 127.6, 126.3, 125.5, 124.1, 122.0, 119.5, 118.3, 114.1.

Example 5: Preparation of 6- (4-ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole Synthesis of Compound [5])

1 mM of biphenylcarboxylic acid contained in 8 to 10 mL of phosphorus oxychloride and 1 mM of compound 1e were refluxed for 5 to 6 hours. The reaction mixture was poured slowly into crushed ice with stirring, which was then neutralized with sodium bicarbonate. The resulting solid material (6- (4-ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole ) Was filtered, washed with cold water and dried to obtain a pink solid (compound [5]) (86%).

Pink solid; Yield: 86%; Rf : 0.53 (chloroform: methanol, 9: 1); IR (? / Cm -1 ): 3018 (sp 2 CH), 2941, 2850 (sp 3 CH), 1578 (C = N), 1540, 1496 (C = C), 1024 (CS); 1H NMR (400 MHz, CDCl 3 ) δ 7.18-7.14 (m, 2H, Ar-H), 6.96-6.93 (m, 2H, Ar-H), 4.51 (s, 2H, CH 2), 4.08-4.12 ( m, 9H, Ferrocene), 3.84 (s, 3H, OCH 3); 13 C NMR (100 MHz, CDCl 3 )? 163.4, 161.0, 160.1, 149.5, 131.2, 129.5, 117.4, 90.1, 88.2, 68.6, 68.1, 67.9, 55.9.

Test Example 1: Evaluation of fluorescent quantum yields of compounds [1] to [5]

To evaluate the effect of solvent polarity on the absorption and release characteristics of the synthesized triazolothiadiazole compound, compounds [1] to [5] each contain chloroform, ethanol, acetonitrile, methanol and dimethylsulfoxide The results for the compounds [1] to [5] are shown in FIGS. 1 to 5 and Table 1 below, respectively.

Comp. Solvents a λ abs ■ nm) b λ em ■ nm) c ε 10 4  ■ M -One cm -One ) d S . shift  ■ cm -One ) e ФFL 6a Chloroform 269 389 19.3 11467 0.006 Ethanol 298 395 17.6 8240 0.0051 Acetonitrile 300 399 15 8270 0.0067 Methanol 237, 301 410 41.6, 23 17803, 8832 0.0071 DMSO 253, 303 415 40.6, 19 15429, 8906 0.010 6b Chloroform 271 410 22 12510 0.0032 Ethanol 304 435 17 9906 0.0053 Acetonitrile 306 438 20.6 9848 0.0061 Methanol 236, 306 441 32.6, 23.3 19697, 10004 0.0084 DMSO 253, 319 449 45.3, 20.6 17253, 9076 0.016 6c Chloroform 252, 265 438 13.6, 13.6 16851, 14904 0.0120 Ethanol 237, 265 440 26.6, 5.3 19466, 15008 0.011 Acetonitrile 253, 262 446 17.6, 17 17104, 15746 0.0121 Methanol 236, 265 447 40.6, 14.3 20001, 15364 0.014 DMSO 263 448 31.3 15701 0.041 6d Chloroform 226, 276, 352 393 37.3, 25.6, 21.6 18802, 10786, 2963 0.130 Ethanol 228, 277, 363 399 39, 25.6, 22 18796, 11038, 2485 0.129 Acetonitrile 227, 278, 366 400 44.3, 36.3, 25 19052, 10971, 2322 0.133 Methanol 254, 277, 367 401 44.3, 32.6, 23 14432, 11163, 2310 0.130 DMSO 239, 280, 374 456 43.3, 27.3, 20 19911, 13784, 4808 0.131 6e Chloroform 275, 318, 431 453 48.3, 18.6, 15.6 14288, 9371, 1126 0.010 Ethanol 275, 320, 435 438 48.3, 18.3, 16.3 13532, 8418, 157 0.009 Acetonitrile 276, 320, 437 459 48.4, 18.3, 16.6 14445, 9463, 1096 0.011 Methanol 278, 326, 437 464 48.4, 19.0, 17.0 14419, 9123, 1331 0.140 DMSO 284, 333, 471 494 48.6, 19.3, 18.3 14968, 9787, 988 0.193

As shown in Table 1 and FIG. 1, the compound [1] synthesized by different solvents had a minimum molar absorption coefficient of 19.3 × 10 4 when chloroform, ethanol and acetonitrile having relatively small polarities were respectively used M -1 cm -1 , 17.6 × 10 4 M -1 cm -1 and 15 × 10 4 M -1 cm -1 , respectively, A single absorption peak appeared in the range of 269 to 300 nm. On the other hand, two distinct absorption signals were observed at 237 ~ 253 nm and 301 ~ 303 nm, and at 41.6 × 10 4 M -1 cm -1 and 40.6 × 10 4 M -1 cm -1 for shorter wavelength signals The coefficients exhibited a high molar absorption coefficient of 23 × 10 4 M -1 cm -1 and 19 × 10 4 M -1 cm -1 in the signals of the longer absorption wavelength range. The largest absorption signal was observed in methanol for compound [1] with a molar absorption coefficient of 41.6 × 10 4 M -1 cm -1 and 23 × 10 4 M -1 cm -1 . Compound [1] has emission spectra ranging from 389 to 415 nm in various solvents with strakes shift values of 8240 to 11467 cm -1 for long wavelength signals and 15429 to 17803 cm -1 for low wavelength signals. On the other hand, the compound [1] exhibited a short wavelength band of 34 nm and a minimum fluorescence quantum number of 0.006 in chloroform and exhibited the largest stover shift of 11467. In addition, the relative fluorescence quantum yield of compound [1] varied from 0.006 to 0.010 in each solvent with various polarities.

As shown in Table 1 and Fig. 2, the compound [2] had a molybdenum absorption coefficient of 22 x 10 4 M -1 cm -1 , 17 x 10 4 M -1 cm -1 , and 20.6 x 10 4 M When using -1 cm -1 of chloroform, ethanol and acetonitrile as the solvent, a single absorption signal appeared in the range of 271 to 306 nm. When methanol and DMSO were used as the solvent, the two absorption signals appeared at 236 nm, 253 nm, 306 nm, and 319 nm, respectively, and 32.6 × 10 4 M -1 cm -1 and 45.3 The molar absorption coefficient of × 10 4 M -1 cm -1 and that of longer wavelength signals were 23.3 × 10 4 M -1 cm -1 and 20.6 × 10 4 M -1 cm -1 , respectively. Compound [2] is the longer wavelength signals in the 9848 cm -1 12510 cm - showed a greater Stowe movement and the short wavelength absorption signal of 17253 cm -1 ~ 19697 cm -1 Stowe greater movement in a first range of 410 ~ 449 nm . In addition, the largest 48 nm shift was observed in chloroform with a minimum quantum yield value of 0.0032, and a maximum quantum yield of 0.016 was observed for compounds using DMSO [2].

In addition, as shown in Table 1 and FIG. 3, compound [3] exhibited one absorption signal at 265 nm, intermediate values of 252 nm and 253 nm in chloroform and acetonitrile, shoulder) signal. On the other hand, ethanol and methanol showed a remarkable additional single signal at the short wavelength interval of 236 nm and 237 nm. In addition, the maximum molal absorption coefficient of 17 × 10 4 M -1 cm -1 was long wavelength in acetonitrile. On the other hand, the maximum molal absorption coefficient of 40.6 × 10 4 M -1 cm -1 appeared in methanol with shorter wavelength. The compound [3] was luminescence showed a 438 ~ 448 nm, respectively Stowe greater movement in the shorter wavelength signal of 16851-20001 cm -1 and the longer wavelength signal in 14904 ~ 15701 cm -1 in the range of. All solvents except DMSO showed a shoulder peak for compound [3]. The compound [3] exhibited a relative fluorescence quantum yield in the range of 0.011 to 0.041. In addition, the maximum quantum yield of 0.041 was obtained in DMSO, while the minimum quantum yield of 0.011 was obtained in ethanol.

As shown in Table 1 and FIG. 4, the compound [4] had a molybdenum absorption coefficient of 37.3 to 44.3 x 10 4 M -1 cm -1 , 25.6 to 36.3 x 10 4 M -1 cm -1, and 21.6 ~ 25 × 10 4 M -1 cm -1 showed three distinct absorption maxima at 226 to 239 nm, 276 to 280 nm and 352 to 374 nm, respectively. In addition, 44.3 × 10 4 M -1 cm -1, 36.3 × 10 4 M -1 cm -1 and 25 × 10 4 M -1 cm - 1, while the maximum absorption coefficient in the observation in the case of using acetonitrile, 37.3 × 10 4 M -1 cm -1 , 25.6 × 10 4 M -1 cm -1 and 21.6 × 10 4 M -1 cm - minimum molar absorption value of 1 was observed in the case of using chloroform. Compound [4] emitted light with a stoichiometric shift of from 14432 to 19911 cm -1 , from 10786 to 13784 cm -1 and from 2310 to 4808 cm -1 , respectively, in the range of 393 to 456 nm. Compound [4] showed an increase in absorption at 12 nm, 14 nm, 15 nm and 24 nm in ethanol, acetonitrile, methanol and DMSO, respectively, in contrast to chloroform. In addition, the highest fluorescence quantum yields of 0.133 and 0.131 were observed in MeCN and DMSO, respectively. While a minimum quantum yield of 0.129 was observed in ethanol.

In addition, as shown in Table 1 and FIG. 5, Compound [5] exhibited three distinct absorption signals with absorption maxima at 275 to 284 nm, 318 to 333 nm and 431 to 471 nm. In addition, it showed three distinct absorption signals of 48.3 ~ 48.6 × 10 4 M -1 cm -1 , 18.6 ~ 19.3 × 10 4 M -1 cm -1 and 15.6 ~ 18.3 × 10 4 M -1 cm -1 , The absorption coefficient was observed in DMSO while the minimum molal absorption coefficient was found in ethanol. The maximum emission of compound [5] was in the range of 453 to 494 nm in various solvents. Compound [5] also exhibited an increase in absorption at 41 nm in DMSO as opposed to chloroform with a maximum quantum yield of 0.193. On the other hand, the quantum yield of compound [5] in various solvents is in the range of 0.009 to 0.193.

For reference, in Table 1, the stoichiometric movement of the triazolothiadiazole compounds of the compounds [1] to [5] synthesized by different solvents is calculated by the following formula 1 and the molar absorption coefficient is calculated by using Beer Lambert's law Respectively.

[Formula 1]

Figure 112015064575759-pat00015

The fluorescence quantum yield ( a? FL) of the compounds [1] to [5] was calculated using the following formula 2, and the results are shown in Table 1 above. As shown in Table 1, all of the compounds [1] to [5] showed excellent quantum yields of fluorescence.

[Formula 2]

Un unk = st std ( I unk / A unk ) ( A std / I std ) ( n unk / n std ) 2

In the above equation, 陸unk represents the fluorescence quantum yield obtained from the samples of the compounds [1] to [5], Φ std represents the standard quantum yield, I unk and I std represent the integrated fluorescence A unk and A std denote the absorbance of the sample and standard at the absorption wavelength, and n unk and n std denote the refractive index of the corresponding solvent.

As shown in Table 1, according to the results of the fluorescence quantum yield data, the quantum yield of the triazolothiadiazole compounds of the compounds [1] to [5] was found to depend entirely on substituents attached to the triazole thiadiazole skeleton Able to know. The relative fluorescence quantum yield of the pyrenyl (compound [4]) or ferrocenyl (compound [5]) substituted for the triazolothiadiazole compound was higher than that of the other compounds (compounds [1] to [3]) . Further, the triazolothiadiazole compound (compound [3]) substituted with p-terphenyl exhibited ordinary fluorescence quantum yield, and the triazolothiadiazole compound (Compound [1]) substituted with biphenyl and naphthyl And compound [2]) showed the lowest fluorescence quantum yield.

Test Example 2: Thermogravimetric analysis

In order to evaluate the thermal stability of the compounds [1] to [5], about 7.85 mg of the compound [1] to the compound [5] was used in the thermal decomposition analysis (TGA) Lt; 0 > C / min, and graphs of the results are shown in Figs. 6A to 6E.

As shown in FIGS. 6A to 6E, the compounds [1] to [4] showed a weight reduction of 20% and showed excellent thermal stability at 300 ° C. or higher. % Weight reduction, but showed a remarkable characteristic only when the temperature was raised to reach 700 ° C by a weight reduction of only 46%.

On the other hand, in the case of the TGA curves of the compounds [1] to [4], an abrupt weight loss was observed at below 100 ° C, which seems to be due to moisture loss.

Further, no compounds were completely decomposed when the temperature was raised to 700 ° C in the compounds [1] to [5].

Therefore, it has been confirmed that the high thermal stability of the compounds can be suitably used for OLED devices and the like.

Test Example 3: Computer model analysis

7 shows the boundary molecular orbital functions of the compounds [1] to [5], i.e., HOMO and LUMO.

As shown in Fig. 7, the electron density distribution pattern in the HOMO and LUMO orbital of all the compounds [1] to [5] did not appear as a straight line. In the HOMO orbitals of the compounds [1] and [3], the electron density is distributed in the triazole ring and the aralkyl ring attached to the fused triazole structure, while the side chain group substituted in the center of the triazole thiadiazole nucleus No electrons cloud was observed in the side chain groups substituted in the fused triazole ring when the electron cloud swelling was reversed in the observed LUMO orbitals.

In addition, electron distribution in the HOMO orbitals of compounds [2] and [4], respectively, as opposed to LUMO orbital, respectively, was also present in the naphthyl group as well as in the pyrenyl ring substituted at the centrally fused heterocyclic nucleus, Electron distribution was observed across the phenyl ring.

On the other hand, the electron distribution pattern was very different for the compound [5]. The electron density is spread across the center fused heterocyclic nucleus as well as the side-connected ferrocenyl groups in the HOMO orbitals of compound [5]. On the other hand, the distribution pattern of electrons in the LUMO orbitals observed electron clouds over the side-connected ferrocenyl groups as well as the methoxy substituents of the aralkyl rings was slightly different.

Claims (10)

A triazolothiadiazole compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
Figure 112017003224418-pat00016

In the above formula, R is any one selected from the group consisting of a biphenyl group, a naphthyl group, a p-terphenyl group, a pyrenyl group, and a perocenyl group.
delete 2. The compound according to claim 1, wherein the triazolothiadiazole compound is
1) 6 - [(1,1'-biphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3 , 4] thiadiazole,
2) Synthesis of 3- (4-methoxybenzyl) -6- (naphthalen-2-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole,
3) 6 - [(1,1 ': 4', 1 "-terphenyl) -4-yl] -3- (4-methoxybenzyl) - [1,2,4] triazolo [ -b] < / RTI > [1,3,4] thiadiazole,
4) Synthesis of 3- (4-methoxybenzyl) -6- (pyrene-4-yl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole, And
5) 6- (4-Ferrocenyl) -3- (4-methoxybenzyl) - [1,2,4] triazolo [3,4- b] [1,3,4] thiadiazole
Wherein the triazolothiadiazole compound is at least one compound selected from the group consisting of:
A composition for fluorescence or luminescence comprising the compound of claim 1 or 3.
(R-COOH) (wherein R is any one selected from the group consisting of a biphenyl group, a naphthyl group, a p-terphenyl group, a pyrenyl group and a ferrocenyl group) and a carboxylic acid And reacting the compound of formula (1) to prepare a triazolothiadiazole compound represented by the formula (1): < EMI ID =
[Chemical Formula 1]
Figure 112017003224418-pat00017

(Wherein R is any one selected from the group consisting of a biphenyl group, a naphthyl group, a p-terphenyl group, a pyrenyl group, and a perocenyl group)
[Formula 1e]
Figure 112017003224418-pat00018
.
delete The compound according to claim 5, wherein the compound represented by formula (1e)
a) reacting a compound represented by the formula (1a) with phosphorus oxychloride to form a compound represented by the following formula (1b);
b) reacting a compound of formula 1b with hydrazine hydrate to form a compound of formula 1c;
c) reacting a compound represented by the following formula (1c) with a carbon disulfide to form a compound represented by the following formula (1d); And
d) reacting a compound represented by the following formula (1d) with hydrazine hydrate to form a compound represented by the following formula
Lt; RTI ID = 0.0 > of: < / RTI &
[Formula 1a]
Figure 112015064575759-pat00019
,

[Chemical Formula 1b]
Figure 112015064575759-pat00020
,

[Chemical Formula 1c]
Figure 112015064575759-pat00021
,

≪ RTI ID = 0.0 &
Figure 112015064575759-pat00022
.
An organic electronic device comprising the triazolothiadiazole compound according to any one of claims 1 to 3.
The organic electronic device according to claim 8, wherein the organic electronic device is an organic light emitting diode (OLED) or a dye-sensitized solar cell (DSSC).
The organic electroluminescent device according to claim 9, wherein the structure of the organic light emitting diode
Anode;
A hole injection layer (HIL) formed on the anode;
A hole transport layer (HTL) formed on the hole injection layer;
An emission layer (EML) formed on the hole transport layer and including a fluorescent dopant comprising the triazole thiadiazole compound of claim 1 or 3;
An electron transport layer (ETL) formed on the light emitting layer; And
A cathode formed on the electron transport layer,
And an organic electroluminescent device.
KR1020150094907A 2015-07-02 2015-07-02 New triazolothiadiazole compound, uses thereof, and organic electroluminescent devices having the same KR101742782B1 (en)

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