TWI702745B - Organic electroluminescent devices and material thereof - Google Patents

Organic electroluminescent devices and material thereof Download PDF

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TWI702745B
TWI702745B TW108131729A TW108131729A TWI702745B TW I702745 B TWI702745 B TW I702745B TW 108131729 A TW108131729 A TW 108131729A TW 108131729 A TW108131729 A TW 108131729A TW I702745 B TWI702745 B TW I702745B
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TW202111977A (en
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王鴻鈞
劉漢康
柯志威
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晶宜科技股份有限公司
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Abstract

A material of the organic electroluminescent devices is provided. The material is a luminescent material and comprises a structure represented by Formula (I):
Figure 01_image001
(I) wherein each Ar 1and Ar 2are individually a substituted or unsubstituted aromatic group from C 6to C 18, or a substituted or unsubstituted heteroaryl group with O atom; R is individually a C 1to C 4alkyl, or a substituted or unsubstituted aromatic group from C 6to C 12.

Description

有機電激發光裝置及其材料Organic electroluminescence device and its material

本發明係關於一種有機電激發光裝置及其材料，特別是指一種可用於有機電激發光裝置之發光層的新穎材料。The present invention relates to an organic electroluminescence device and its materials, and particularly to a novel material that can be used in the light-emitting layer of the organic electroluminescence device.

有機發光二極體(organic light-emitting diodes，OLEDs)係應用有機電激發光(organic electroluminescence，OEL)原理製造的發光元件。其發光原理是指在一定電場下，使電子電洞分別經過電洞傳輸層(Hole Transport Layer, HTL)與電子傳輸層(Electron Transport Layer, ETL)後，進入一具有發光特性的有機物質(有機發光層)。當電子與電洞在此發光層內發生再結合時，會先形成一「激發光子(exciton)」，接著再將能量釋放出來而回到基態(ground state)，而這些釋放出來的能量會有部份以不同顏色的光的形式釋放出來，使OLED發光。Organic light-emitting diodes (OLEDs) are light-emitting elements manufactured using the principle of organic electroluminescence (OEL). The principle of light emission means that under a certain electric field, the electron holes pass through the Hole Transport Layer (HTL) and the Electron Transport Layer (ETL) respectively, and then enter an organic substance with light-emitting characteristics (organic Luminescent layer). When electrons and holes recombine in this light-emitting layer, they will first form an "exciton", and then release the energy to return to the ground state, and the released energy will have Part of it is released in the form of light of different colors to make the OLED emit light.

常用的OLED元件以客體(Dopant)發光材料，混合摻入單一主體(Host)發光材料中，使元件呈現出不同的顏色。Commonly used OLED devices use a Dopant light-emitting material, mixed into a single host (Host) light-emitting material, so that the device exhibits different colors.

目前市面上已有如C545T (Coumarin 545T，CAS: 155306-71-1，玻璃轉移溫度Tg≒100℃)之類的綠色客體材料，但其仍有壽命短和發光效率較低的問題。因此，開發更優良的發光材料一直是所有相關廠商努力的目標。At present, there are already green guest materials such as C545T (Coumarin 545T, CAS: 155306-71-1, glass transition temperature Tg≒100°C) on the market, but they still have the problems of short life and low luminous efficiency. Therefore, the development of better luminescent materials has always been the goal of all relevant manufacturers.

本發明提供一種有機電激發光裝置之材料，其化合物結構與產品特性均與先前技術不同，為新穎之發明。The present invention provides a material for an organic electroluminescence device, the compound structure and product characteristics of which are different from those of the prior art, which is a novel invention.

根據本發明之一實施例，提供一種有機電激發光裝置之材料。此材料係具有下列化學式(I)所示之結構：

Figure 02_image001
(I)； According to an embodiment of the present invention, a material for an organic electroluminescence device is provided. This material has the structure shown in the following chemical formula (I):
Figure 02_image001
(I);

其中，Ar 1與Ar 2各自獨立為經取代的C 6至C 18芳基、未取代的C 6至C 18芳基、經取代的含有氧原子之雜芳基或未取代的含有氧原子之雜芳基，R各自獨立為C 1至C 4烷基、經取代的C 6至C 12芳基或未取代的C 6至C 12芳基。 Wherein, Ar 1 and Ar 2 are each independently a substituted C 6 to C 18 aryl group, an unsubstituted C 6 to C 18 aryl group, a substituted oxygen atom-containing heteroaryl group, or an unsubstituted oxygen atom-containing group In the heteroaryl group, R is each independently a C 1 to C 4 alkyl group, a substituted C 6 to C 12 aryl group, or an unsubstituted C 6 to C 12 aryl group.

一實施例中， Ar 1與Ar 2各自獨立為經取代或未取代的

Figure 02_image003
、
Figure 02_image005
或
Figure 02_image007
，且A各自獨立為H、C 1至C 4的烷基或苯。 In one embodiment, Ar 1 and Ar 2 are each independently substituted or unsubstituted
Figure 02_image003
,
Figure 02_image005
or
Figure 02_image007
, And A is each independently H, a C 1 to C 4 alkyl group, or benzene.

一實施例中，上述材料係具有下列化學式中任一者所示之結構：

Figure 02_image009
Figure 02_image011
Figure 02_image013
 GD1-1 GD1-2 GD1-3      
Figure 02_image015
Figure 02_image017
Figure 02_image019
 GD1-4 GD1-5 GD1-6      
Figure 02_image021
Figure 02_image023
Figure 02_image025
 GD1-7 GD1-8 GD1-9      
Figure 02_image027
Figure 02_image029
Figure 02_image031
 GD1-10 GD1-11 GD1-12      
Figure 02_image033
Figure 02_image035
Figure 02_image037
 GD1-13 GD1-14 GD1-15      
Figure 02_image039
Figure 02_image041
Figure 02_image043
 GD1-16 GD1-17 GD1-18      
Figure 02_image045
Figure 02_image047
Figure 02_image049
 GD1-19 GD1-20 GD1-21      
Figure 02_image051
Figure 02_image053
Figure 02_image055
 GD1-22 GD1-23 GD1-24      
Figure 02_image057
Figure 02_image059
Figure 02_image061
 GD2-1 GD2-2 GD2-3      
Figure 02_image063
Figure 02_image065
Figure 02_image067
 GD2-4 GD2-5 GD2-6      
Figure 02_image069
Figure 02_image071
Figure 02_image073
 GD2-7 GD2-8 GD2-9      
Figure 02_image075
Figure 02_image077
Figure 02_image079
 GD2-10 GD2-11 GD2-12      
Figure 02_image081
Figure 02_image083
Figure 02_image085
 GD2-13 GD2-14 GD2-15      
Figure 02_image087
Figure 02_image089
Figure 02_image091
 GD3-1 GD3-2 GD3-3      
Figure 02_image093
Figure 02_image095
Figure 02_image097
 GD3-4 GD3-5 GD3-6      
Figure 02_image099
Figure 02_image101
Figure 02_image103
 GD3-7 GD3-8 GD3-9      
Figure 02_image105
Figure 02_image107
Figure 02_image109
 GD4-1 GD4-2 GD4-3      
Figure 02_image111
Figure 02_image113
Figure 02_image115
 GD4-4 GD4-5 GD4-6      
Figure 02_image117
Figure 02_image119
Figure 02_image121
 GD4-7 GD4-8 GD4-9               。 In one embodiment, the above-mentioned material has a structure shown in any one of the following chemical formulas:
Figure 02_image009
Figure 02_image011
Figure 02_image013
 GD1-1 GD1-2 GD1-3
Figure 02_image015
Figure 02_image017
Figure 02_image019
 GD1-4 GD1-5 GD1-6
Figure 02_image021
Figure 02_image023
Figure 02_image025
 GD1-7 GD1-8 GD1-9
Figure 02_image027
Figure 02_image029
Figure 02_image031
 GD1-10 GD1-11 GD1-12
Figure 02_image033
Figure 02_image035
Figure 02_image037
 GD1-13 GD1-14 GD1-15
Figure 02_image039
Figure 02_image041
Figure 02_image043
 GD1-16 GD1-17 GD1-18
Figure 02_image045
Figure 02_image047
Figure 02_image049
 GD1-19 GD1-20 GD1-21
Figure 02_image051
Figure 02_image053
Figure 02_image055
 GD1-22 GD1-23 GD1-24
Figure 02_image057
Figure 02_image059
Figure 02_image061
 GD2-1 GD2-2 GD2-3
Figure 02_image063
Figure 02_image065
Figure 02_image067
 GD2-4 GD2-5 GD2-6
Figure 02_image069
Figure 02_image071
Figure 02_image073
 GD2-7 GD2-8 GD2-9
Figure 02_image075
Figure 02_image077
Figure 02_image079
 GD2-10 GD2-11 GD2-12
Figure 02_image081
Figure 02_image083
Figure 02_image085
 GD2-13 GD2-14 GD2-15
Figure 02_image087
Figure 02_image089
Figure 02_image091
 GD3-1 GD3-2 GD3-3
Figure 02_image093
Figure 02_image095
Figure 02_image097
 GD3-4 GD3-5 GD3-6
Figure 02_image099
Figure 02_image101
Figure 02_image103
 GD3-7 GD3-8 GD3-9
Figure 02_image105
Figure 02_image107
Figure 02_image109
 GD4-1 GD4-2 GD4-3
Figure 02_image111
Figure 02_image113
Figure 02_image115
 GD4-4 GD4-5 GD4-6
Figure 02_image117
Figure 02_image119
Figure 02_image121
 GD4-7 GD4-8 GD4-9.

一實施例中，上述材料之發光波長介於500至535 nm。In one embodiment, the emission wavelength of the above-mentioned materials is between 500 and 535 nm.

一實施例中，上述材料其係作為有機電激發光裝置之發光客體。In one embodiment, the above-mentioned material is used as the light-emitting object of the organic electroluminescence device.

根據本發明另一實施例，提供一種有機電激發光裝置，其係包含依以下順序排列之層狀結構：透明基板、陽極層、電洞傳輸層、發光層、電子傳輸層及陰極層。此有機電激發光裝置之特徵在於其發光層中包含上述之材料。According to another embodiment of the present invention, an organic electroluminescent device is provided, which includes a layered structure arranged in the following order: a transparent substrate, an anode layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer. The organic electroluminescence device is characterized in that the light-emitting layer contains the above-mentioned materials.

一實施例中，有機電激發光裝置之陽極層和電洞傳輸層之間係進一步包含一電洞注入層。In one embodiment, a hole injection layer is further included between the anode layer and the hole transport layer of the organic electroluminescence device.

一實施例中，有機電激發光裝置之電子傳輸層和陰極層之間係進一步包含一電子注入層。In one embodiment, the organic electroluminescence device further includes an electron injection layer between the electron transport layer and the cathode layer.

一實施例中，有機電激發光裝置之電子傳輸層和發光層之間係進一步包含一電洞阻擋層。In one embodiment, the organic electroluminescent device further includes a hole blocking layer between the electron transport layer and the light emitting layer.

一實施例中，有機電激發光裝置之陽極層和陰極層係分別與一外部電源接觸形成電通路。In one embodiment, the anode layer and the cathode layer of the organic electroluminescence device are respectively in contact with an external power source to form electrical paths.

相較於習知之發光客體材料，本發明上述新穎材料的玻璃轉移溫度(Tg)高，應用於工業製程時有較佳熱穩定性，且具有容易製備與純化等優點。此新穎材料的發光效率及功率效率亦更佳，使用其作為發光客體材料的有機電激發光裝置，與使用習知發光客體材料的有機電激發光裝置相比，具有更高的元件效率。Compared with conventional luminescent guest materials, the novel materials of the present invention have a higher glass transition temperature (Tg), have better thermal stability when applied to industrial processes, and have the advantages of easy preparation and purification. The luminous efficiency and power efficiency of this novel material are also better. The organic electroluminescent device using it as the luminescent guest material has higher element efficiency than the organic electroluminescent device using the conventional luminescent guest material.

本發明提供一種有機電激發光裝置之材料，具有下列化學式(I)所示之結構：

Figure 02_image001
(I)； The present invention provides a material for an organic electroluminescence device, which has the structure shown in the following chemical formula (I):
Figure 02_image001
(I);

其中，Ar 1與Ar 2各自獨立為經取代的C 6至C 18芳基、未取代的C 6至C 18芳基、經取代的含有氧原子之雜芳基或未取代的含有氧原子之雜芳基，R各自獨立為C 1至C 4烷基、經取代的C 6至C 12芳基或未取代的C 6至C 12芳基。 Wherein, Ar 1 and Ar 2 are each independently a substituted C 6 to C 18 aryl group, an unsubstituted C 6 to C 18 aryl group, a substituted oxygen atom-containing heteroaryl group, or an unsubstituted oxygen atom-containing group In the heteroaryl group, R is each independently a C 1 to C 4 alkyl group, a substituted C 6 to C 12 aryl group, or an unsubstituted C 6 to C 12 aryl group.

進一步來說， Ar 1與Ar 2可獨立為經取代或未取代的

Figure 02_image003
、
Figure 02_image005
或
Figure 02_image007
，其中A各自獨立為H、C 1至C 4的烷基或苯。 Furthermore, Ar 1 and Ar 2 can be independently substituted or unsubstituted
Figure 02_image003
,
Figure 02_image005
or
Figure 02_image007
, Wherein A is each independently H, C 1 to C 4 alkyl or benzene.

本文中「經取代」的取代基，係指該取代基上的可鍵結位置由1個以上的C 1至C 4烷基所取代。舉例來說，若-Ar 1為苯，由於其已與N鍵結佔用一個位置，故「經取代」的Ar 1可為1至5個C 1至C 4烷基所取代的苯。 The "substituted" substituent herein means that the bondable position on the substituent is substituted by more than one C 1 to C 4 alkyl group. For example, if -Ar 1 is benzene, the "substituted" Ar 1 can be benzene substituted with 1 to 5 C 1 to C 4 alkyl groups because it has already been bonded to N and occupies a position.

Ar之結構中，以波浪線﹏標示的鍵結，表示Ar與N的連結位置。而***環中心的鍵結，表示此鍵結的位置不固定，可位於該些環上的任意可鍵結位置。舉例來說，

Figure 02_image005
表示N可鍵結在
Figure 02_image123
4個位置其中之一(左右對稱)，而
Figure 02_image007
表示N可鍵結
Figure 02_image125
在4個位置其中之一。 In the Ar structure, the bond marked with a wavy line ﹏ indicates the connection position of Ar and N. The bond inserted into the center of the ring means that the position of the bond is not fixed and can be located at any bondable position on the rings. for example,
Figure 02_image005
Indicates that N can be bonded in
Figure 02_image123
One of 4 positions (symmetrical left and right), and
Figure 02_image007
Represents N bondable
Figure 02_image125
In one of 4 positions.

式(I)材料例如可由以下之合成方法獲得： 第 1 步： Suzuki coupling 偶聯反應

Figure 02_image127
第 2 步：合環反應
Figure 02_image129
第 3 步：溴化反應
Figure 02_image131
第 4 步： Buchwald-hartwig Coupling 偶聯反應
Figure 02_image133
The material of formula (I) can be obtained, for example, by the following synthesis method: Step 1 : Suzuki coupling reaction
Figure 02_image127
Step 2 : Closing reaction
Figure 02_image129
Step 3 : Bromination reaction
Figure 02_image131
Step 4 : Buchwald-hartwig Coupling coupling reaction
Figure 02_image133

上述合成方法使用的Suzuki偶聯、合環、溴化及Buchwald-hartwig 偶聯反應，皆為工業應用上常見的有機合成反應。使用上述反應進行合成，反應時間短且製備容易，且副產物生成少，純化難度較低。The Suzuki coupling, ring closure, bromination, and Buchwald-hartwig coupling reactions used in the above-mentioned synthesis methods are all common organic synthesis reactions in industrial applications. The above reaction is used for synthesis, the reaction time is short and the preparation is easy, and the by-products are less generated and the purification difficulty is low.

以下藉由數個應用實施例說明上述反應的各個步驟。然需特別注意的是，實施例中化合物添加的成分比例及種類僅為示範之用，並非用以限制本發明。 實施例 1 ：中間體 A (Intermediate A) 之合成

Figure 02_image135
Hereinafter, several application examples are used to illustrate each step of the above reaction. However, it should be particularly noted that the proportions and types of the added components of the compounds in the examples are for demonstration purposes only, and are not intended to limit the present invention. Example 1 : Synthesis of Intermediate A
Figure 02_image135

1L三頸瓶置入26.6克1-芘硼酸、25.8克1-溴-2-萘甲酸甲酯，與27.7克碳酸鉀(Potassium carbonate)，置於氮氣系統下，加入300毫升甲苯(Tol)/ 100毫升去離子水/ 10毫升乙醇，攪拌溶解後再加入5.8克四(三苯基膦)鈀 Tetrakis(triphenylphosphine)palladium(0)，加熱迴流反應6小時。冷卻後分離有機層，並使用150毫升甲苯萃取水層2次，合併有機層並進行濃縮，濃縮後的膠體使用乙酸乙酯/正己烷進行再結晶，過濾得白色固體，烘乾得中間體A成品32 克，產率80% 。A 1L three-necked flask was placed in 26.6 g of 1-pyrene boric acid, 25.8 g of methyl 1-bromo-2-naphthoate, and 27.7 g of potassium carbonate (Potassium carbonate), placed under a nitrogen system, and added 300 ml of toluene (Tol)/ 100ml of deionized water/10ml of ethanol, stir to dissolve, add 5.8g of Tetrakis(triphenylphosphine)palladium(0), heat and reflux for 6 hours. After cooling, the organic layer was separated, and the aqueous layer was extracted twice with 150 ml of toluene. The organic layers were combined and concentrated. The concentrated colloid was recrystallized with ethyl acetate/n-hexane, filtered to obtain a white solid, and dried to obtain Intermediate A The finished product is 32 grams, and the yield is 80%.

本步驟為[0024]段所述之第1步：Suzuki coupling偶聯反應。 實施例 2 ：中間體 B1 (Intermediate B1) 之合成

Figure 02_image137
This step is the first step described in paragraph [0024]: Suzuki coupling reaction. Example 2 : Synthesis of Intermediate B1 (Intermediate B1)
Figure 02_image137

1L三頸瓶置入30.8克中間體 A，置於氮氣系統下，加入400毫升四氫呋喃(THF)，攪拌溶解後降溫至-85℃，滴入125毫升1.6M甲基鋰(Methyllithium)，攪拌30分鐘，移除低溫槽攪拌3小時。加水中止反應後，使用乙酸乙酯進行萃取，收集有機層並濃縮，加入200毫升醋酸與20毫升鹽酸，加熱迴流1hr，冷卻後加入甲醇，固體析出並收集固體，進行管柱分離(Hex:THF=15:1)，濃縮過濾得黃色固體，烘乾得中間體 B1成品22 克，產率75%。Place 30.8 g of Intermediate A in a 1L three-necked flask, place it under a nitrogen system, add 400 ml of tetrahydrofuran (THF), stir to dissolve and then cool to -85℃, drop in 125 ml of 1.6M methyllithium (Methyllithium), and stir for 30 Minutes, remove the low temperature tank and stir for 3 hours. After adding water to stop the reaction, extract with ethyl acetate, collect the organic layer and concentrate, add 200 ml of acetic acid and 20 ml of hydrochloric acid, heat to reflux for 1 hr, add methanol after cooling, solids precipitate and collect solids, and carry out column separation (Hex:THF =15:1), concentrated and filtered to obtain a yellow solid, dried to obtain 22 grams of intermediate B1 finished product, the yield was 75%.

本步驟為[0024]段所述之第2步：合環反應。 實施例 3 ：中間體 C1/C2 (Intermediate C1/C2) 之合成

Figure 02_image139
This step is the second step described in paragraph [0024]: ring closure reaction. Synthesis of Intermediate C1 / C2 (Intermediate C1 / C2 ) of: Example 3
Figure 02_image139

1L 三頸瓶置入18.4克中間體 B1，置於氮氣系統下，加入300毫升1,2-二氯乙烷(DCE)攪拌溶解，加入16.6克N-溴代丁二醯亞胺(NBS)室溫下攪拌3 hr，加入甲醇逼出過濾並收集固體，固體進行1,2-二氯乙烷(DCE)再結晶，過濾得黃色固體，收得中間體C1產物12克，產率46%。再結晶濾液濃縮收集固體，進行管柱分離(Hex:THF=15:1)，濃縮過濾得黃色固體，收得中間體C2產物13克，產率49%Place 18.4 g of intermediate B1 in a 1L three-necked flask, place it under a nitrogen system, add 300 ml of 1,2-dichloroethane (DCE) and stir to dissolve, add 16.6 g of N-bromosuccinimide (NBS) Stir at room temperature for 3 hr, add methanol to force out the filter and collect the solid. The solid is recrystallized with 1,2-dichloroethane (DCE), and a yellow solid is obtained by filtration. The intermediate C1 product is 12 grams, and the yield is 46%. . The recrystallized filtrate was concentrated to collect the solid, and the column was separated (Hex:THF=15:1), concentrated and filtered to obtain a yellow solid, and 13 g of intermediate C2 product was obtained, the yield was 49%

本步驟為[0024]段所述之第3步：溴化反應。 實施例 4 ：中間體 B2 (Intermediate B2) 之合成

Figure 02_image141
This step is the third step described in paragraph [0024]: bromination reaction. Example 4 : Synthesis of Intermediate B2
Figure 02_image141

0.5L三頸瓶置入15.4克中間體 A，置於氮氣系統下，加入200毫升四氫呋喃(THF)，攪拌溶解後降溫至-85℃，滴入52毫升1.9M苯基鋰(Phenyllithium)，攪拌30分鐘，移除低溫槽攪拌3小時，加水中止反應後，使用乙酸乙酯進行萃取，收集有機層並濃縮，加入100毫升醋酸與10毫升鹽酸，加熱迴流1hr，冷卻後加入甲醇，固體析出並收集固體，進行管柱分離(Hex:THF=12:1)，濃縮過濾得黃色固體，烘乾得中間體 B2成品12 克，產率63%。Put 15.4 g of Intermediate A in a 0.5L three-necked flask, place it under a nitrogen system, add 200 ml of tetrahydrofuran (THF), stir to dissolve and then cool to -85°C, drop 52 ml of 1.9M phenyllithium (Phenyllithium), and stir After 30 minutes, remove the low temperature tank and stir for 3 hours. After adding water to stop the reaction, extract with ethyl acetate, collect the organic layer and concentrate, add 100 ml of acetic acid and 10 ml of hydrochloric acid, heat to reflux for 1 hour, add methanol after cooling, solids precipitate out and The solids were collected, separated by column (Hex:THF=12:1), concentrated and filtered to obtain a yellow solid, dried to obtain 12 grams of intermediate B2 finished product, with a yield of 63%.

本步驟為[0024]段所述之第2步：合環反應。 實施例 5 ：中間體 C3/C4 (Intermediate C3/C4) 之合成

Figure 02_image143
This step is the second step described in paragraph [0024]: ring closure reaction. Intermediate C3 / C4 (Intermediate C3 / C4 ) of Synthesis Example 5:
Figure 02_image143

1L 三頸瓶置入9.8克中間體 B2，置於氮氣系統下，加入100毫升1,2-二氯乙烷(DCE)攪拌溶解，加入7.0克N-溴代丁二醯亞胺(NBS)室溫下攪拌3 hr，加入甲醇逼出過濾收集固體，固體進行1,2-二氯乙烷(DCE)再結晶，過濾得黃色固體，收得中間體C3產物5.3克，產率41%。再結晶濾液濃縮收集固體，進行管柱分離(Hex:THF=15:1)，濃縮過濾得黃色固體，收得中間體C4產物5.7克，產率44%。Place 9.8 g of intermediate B2 in a 1L three-necked flask, place it under a nitrogen system, add 100 ml of 1,2-dichloroethane (DCE) and stir to dissolve, add 7.0 g of N-bromosuccinimide (NBS) Stir at room temperature for 3 hrs, add methanol to force out the solids by filtration and collect the solids. Recrystallize the solids with 1,2-dichloroethane (DCE), and filter to obtain yellow solids. The intermediate C3 product is 5.3 g with a yield of 41%. The recrystallized filtrate was concentrated to collect the solid, and subjected to column separation (Hex:THF=15:1), concentrated and filtered to obtain a yellow solid, and 5.7 g of intermediate C4 product was obtained with a yield of 44%.

本步驟為[0024]段所述之第3步：溴化反應。 實施例 6 ： GD1-2 之合成

Figure 02_image145
This step is the third step described in paragraph [0024]: bromination reaction. Example 6 : Synthesis of GD1-2
Figure 02_image145

在氮氣下於三頸瓶中置入2.6克中間體C1(Intermediate C1)與1.9克4-甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.7克第三丁醇鉀，0.11克乙酸鈀，0.26克三叔丁基膦，加熱迴流反應2小時，冷卻濃縮後析出固體，固體以四氫呋喃(THF)再結晶2次，過濾得產物2.5克，純度99%，產率68%。經昇華純化後得2.1克產物。Under nitrogen, put 2.6 g of Intermediate C1 (Intermediate C1) and 1.9 g of 4-methyldiphenylamine, 40 ml of toluene (Tol) into a three-necked flask, stir to dissolve, add 1.7 g of potassium tert-butoxide and 0.11 g of palladium acetate , 0.26 g of tri-tert-butyl phosphine, heated and refluxed for 2 hours, cooled and concentrated to precipitate a solid, which was recrystallized twice with tetrahydrofuran (THF), filtered to obtain 2.5 g of the product, with a purity of 99% and a yield of 68%. 2.1 g of product was obtained after purification by sublimation.

本步驟為[0024]段所述之第4步：Buchwald-hartwig 偶聯反應，產物GD1-2之NMR圖譜及質譜檢測結果如下：This step is the fourth step described in paragraph [0024]: Buchwald-hartwig coupling reaction. The NMR spectrum and mass spectrometry results of the product GD1-2 are as follows:

1H NMR (400MHz, CDCl 3)：δ8.88(d, 1H), δ8.79(d, 1H), 8.33-7.85(m, 7H), δ7.73-7.52(m, 4H), δ7.45-7.06(m, 10H), δ6.95-6.62(m, 7H) , δ2.20(s, 3H) , δ2.08(s, 3H) , δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.88(d, 1H), δ8.79(d, 1H), 8.33-7.85(m, 7H), δ7.73-7.52(m, 4H), δ7. 45-7.06(m, 10H), δ6.95-6.62(m, 7H), δ2.20(s, 3H), δ2.08(s, 3H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 55H 42N 2for, 730.3；found,730.3 實施例 7 ： GD1-5 之合成

Figure 02_image147
MS (m/z): [M + ] calcd. C 55 H 42 N 2 for, 730.3; found, 730.3 Example 7 : Synthesis of GD1-5
Figure 02_image147

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為2.1克4,4'-二甲基二苯胺，可製備GD1-5成品2.7克，純度99%，產率71%。經昇華純化後得2.3克產物。Following the synthetic procedure in compound GD1-2, changing 1.9 g of 4-methyldiphenylamine to 2.1 g of 4,4'-dimethyldiphenylamine, 2.7 g of finished product of GD1-5 can be prepared with a purity of 99% and a yield of 71 %. After purification by sublimation, 2.3 grams of product were obtained.

1H NMR (400MHz, CDCl 3)：δ8.87(d, 2H), δ8.21-8.02(m, 5H), 7.96(d, 1H), δ7.77(d, 1H), δ7.56(t, 1H), δ7.51-7.33(m, 2H), δ7.10-6.91(m, 16H) , δ2.28(d, 12H) , δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.87(d, 2H), δ8.21-8.02(m, 5H), 7.96(d, 1H), δ7.77(d, 1H), δ7.56( t, 1H), δ7.51-7.33(m, 2H), δ7.10-6.91(m, 16H), δ2.28(d, 12H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 57H 46N 2for, 758.4；found,758.4 實施例 8 ： GD1-8 之合成

Figure 02_image149
MS (m/z): [M + ] calcd. C 57 H 46 N 2 for, 758.4; found, 758.4 Example 8 : Synthesis of GD1-8
Figure 02_image149

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為2.4克双(3,4-二甲苯基)胺，可製備GD1-8成品3.2克，純度99%，產率78%。經昇華純化後得2.9克產物。Following the synthetic procedure in compound GD1-2, replacing 1.9 g of 4-methyldiphenylamine with 2.4 g of bis(3,4-xylyl)amine, 3.2 g of GD1-8 product can be prepared with a purity of 99% and a yield 78%. After purification by sublimation, 2.9 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.88(d, 1H), δ8.81(d, 1H), 8.22-8.06(m, 5H), δ7.97(d, 1H), δ7.77(d, 1H), δ7.56(m, 1H) , δ7.49(s, 1H) , δ7.39(m, 1H) , δ6.99-6.73(m, 12H) , 2.18(d, 12H), δ2.13(d, 12H), δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.88(d, 1H), δ8.81(d, 1H), 8.22-8.06(m, 5H), δ7.97(d, 1H), δ7.77( d, 1H), δ7.56(m, 1H), δ7.49(s, 1H), δ7.39(m, 1H), δ6.99-6.73(m, 12H), 2.18(d, 12H), δ2.13(d, 12H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 61H 54N 2for, 814.4；found,814.4 實施例 9 ： GD1-9 之合成

Figure 02_image151
MS (m/z): [M + ] calcd. C 61 H 54 N 2 for, 814.4; found, 814.4 Example 9 : Synthesis of GD1-9
Figure 02_image151

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為2.4克N-(對甲苯基)-2-萘胺，可製備GD1-9成品3.1克，純度99%，產率74%。經昇華純化後得2.6克產物。Following the synthetic procedure in compound GD1-2, replacing 1.9 g of 4-methyldiphenylamine with 2.4 g of N-(p-tolyl)-2-naphthylamine, 3.1 g of GD1-9 product can be prepared with a purity of 99%. The rate is 74%. After purification by sublimation, 2.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.91(d, 1H), δ8.85(d, 1H), 8.23-8.10(m, 5H), δ7.95(d, 1H), δ7.84(d, 1H), δ7.77-7.52(m, 10H), 7.17-7.11(m, 8H) , δ2.32(d, 6H) , δ1.59(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.91(d, 1H), δ8.85(d, 1H), 8.23-8.10(m, 5H), δ7.95(d, 1H), δ7.84( d, 1H), δ7.77-7.52(m, 10H), 7.17-7.11(m, 8H), δ2.32(d, 6H), δ1.59(s, 6H).

MS (m/z)：[M +] calcd. C 63H 46N 2for, 830.4；found,830.4 實施例 10 ： GD1-10 之合成

Figure 02_image153
MS (m/z): [M + ] calcd. C 63 H 46 N 2 for, 830.4; found, 830.4 Example 10 : Synthesis of GD1-10
Figure 02_image153

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為2.3克N-苯基-2-萘胺，可製備GD1-10成品2.4克，純度99%，產率69%。經昇華純化後得2.0克產物。Following the synthetic procedure in compound GD1-2, replacing 1.9 g of 4-methyldiphenylamine with 2.3 g of N-phenyl-2-naphthylamine, 2.4 g of GD1-10 finished product can be prepared with a purity of 99% and a yield of 69% . After purification by sublimation, 2.0 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.91(d, 1H), δ8.85(d, 1H) , δ8.23-8.12(m, 5H) , δ7.96(d, 1H), δ7.85(d, 1H), δ7.78-7.67(m, 4H), δ7.62-7.53(m, 3H) , δ7.50-7.11(m, 18H), δ7.03-6.95(m, 2H) , δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.91(d, 1H), δ8.85(d, 1H), δ8.23-8.12(m, 5H), δ7.96(d, 1H), δ7. 85(d, 1H), δ7.78-7.67(m, 4H), δ7.62-7.53(m, 3H), δ7.50-7.11(m, 18H), δ7.03-6.95(m, 2H) , δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 61H 42N 2for, 802.3；found, 802.3 實施例 11 ： GD1-12 之合成

Figure 02_image155
MS (m/z): [M + ] calcd. C 61 H 42 N 2 for, 802.3; found, 802.3 Example 11 : Synthesis of GD1-12
Figure 02_image155

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為2.8克2,2'-二萘胺，可製備GD1-12成品3.0克，純度99%，產率66%。經昇華純化後得2.4克產物。Following the synthetic procedure in compound GD1-2, changing 1.9 g of 4-methyldiphenylamine to 2.8 g of 2,2'-dinaphthylamine, 3.0 g of finished GD1-12 can be prepared with a purity of 99% and a yield of 66%. 2.4 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.95(d, 1H), δ8.88(d, 1H) , δ8.25-8.13(m, 5H) , δ7.95(d, 1H), 7.89(d, 1H), δ7.80-7.69(m, 8H), δ7.61-7.57(m, 3H) , δ7.52-7.28(m, 20H), δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.95(d, 1H), δ8.88(d, 1H), δ8.25-8.13(m, 5H), δ7.95(d, 1H), 7.89( d, 1H), δ7.80-7.69(m, 8H), δ7.61-7.57(m, 3H), δ7.52-7.28(m, 20H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 69H 46N 2for, 902.4；found, 902.3 實施例 12 ： GD1-15 之合成

Figure 02_image157
MS (m/z): [M + ] calcd. C 69 H 46 N 2 for, 902.4; found, 902.3 Example 12 : Synthesis of GD1-15
Figure 02_image157

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為3.0克二(4-聯苯基)胺，可製備GD1-15成品3.1克，純度99%，產率62%。經昇華純化後得2.4克產物。Following the synthetic procedure in compound GD1-2, replacing 1.9 g of 4-methyldiphenylamine with 3.0 g of bis(4-biphenyl)amine, 3.1 g of finished GD1-15 can be prepared, with a purity of 99% and a yield of 62% . 2.4 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.93(d, 1H), δ8.88(d, 1H) , δ8.27-8.08(m, 5H) , δ8.04(d, 1H), 7.91(d, 1H), δ7.65-7.35(m, 27H) , δ7.31-7.18(m, 12H), δ1.63(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.93(d, 1H), δ8.88(d, 1H), δ8.27-8.08(m, 5H), δ8.04(d, 1H), 7.91( d, 1H), δ7.65-7.35(m, 27H), δ7.31-7.18(m, 12H), δ1.63(s, 6H).

MS (m/z)：[M +] calcd. C 77H 54N 2for, 1006.4；found, 1006.3 實施例 13 ： GD1-19 之合成

Figure 02_image159
MS (m/z): [M + ] calcd. C 77 H 54 N 2 for, 1006.4; found, 1006.3 Example 13 : Synthesis of GD1-19
Figure 02_image159

依循化合物GD1-2中之合成程序，將1.9克4-甲基二苯胺改換為3.0克N-(3,4-二甲基苯基)-4-二苯並呋喃基胺，可製備GD1-19成品2.8克，純度99%，產率59%。經昇華純化後得2.1克產物。Following the synthetic procedure in compound GD1-2, 1.9 g of 4-methyldiphenylamine was changed to 3.0 g of N-(3,4-dimethylphenyl)-4-dibenzofuranylamine to prepare GD1- The finished product of 19 is 2.8 grams, the purity is 99%, and the yield is 59%. 2.1 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.87(d, 1H), δ8.84(d, 1H) , δ8.29-8.02(m, 5H) , δ7.98-7.86(m, 4H), 7.72-7.63(m, 3H), δ7.40-7.06(m, 12H), δ6.98-6.62(m, 6H) , δ2.29-2.05(m, 12H), δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.87(d, 1H), δ8.84(d, 1H), δ8.29-8.02(m, 5H), δ7.98-7.86(m, 4H), 7.72-7.63(m, 3H), δ7.40-7.06(m, 12H), δ6.98-6.62(m, 6H), δ2.29-2.05(m, 12H), δ1.58(s, 6H) .

MS (m/z)：[M +] calcd. C 69H 50N 2O 2for, 938.4；found, 938.3 實施例 14 ： GD2-3 之合成

Figure 02_image161
MS (m/z): [M + ] calcd. C 69 H 50 N 2 O 2 for, 938.4; found, 938.3 Example 14 : Synthesis of GD2-3
Figure 02_image161

在氮氣下於三頸瓶中置入2.6克中間體C2(Intermediate C2)與2.1克4,4'-二甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.7克第三丁醇鉀，0.11克乙酸鈀，0.26克三叔丁基膦，加熱迴流反應2小時，冷卻濃縮後析出固體，固體以四氫呋喃/乙酸乙酯(THF/EA)再結晶2次，過濾得產物2.2克，純度99%，產率58%。經昇華純化後得1.6克產物。Place 2.6 g of Intermediate C2 (Intermediate C2) and 2.1 g of 4,4'-dimethyldiphenylamine, 40 ml of toluene (Tol) in a three-necked flask under nitrogen, and add 1.7 g of potassium tert-butoxide, 0.11 g of palladium acetate, 0.26 g of tri-tert-butyl phosphine, heated at reflux for 2 hours, cooled and concentrated, a solid precipitated out, and the solid was recrystallized twice with tetrahydrofuran/ethyl acetate (THF/EA), filtered to obtain 2.2 g of product, with a purity of 99 %, the yield is 58%. After purification by sublimation, 1.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.73(d, 1H), δ8.70(d, 1H) , δ8.20-8.01(m, 5H) , δ7.78(d, 1H), δ7.52-7.31(m, 2H), δ7.03-6.87(m, 18H), δ2.27(d, 12H) , δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.73(d, 1H), δ8.70(d, 1H), δ8.20-8.01(m, 5H), δ7.78(d, 1H), δ7. 52-7.31(m, 2H), δ7.03-6.87(m, 18H), δ2.27(d, 12H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 57H 46N 2for, 758.4；found, 758.4 實施例 15 ： GD2-6 之合成

Figure 02_image163
MS (m/z): [M + ] calcd. C 57 H 46 N 2 for, 758.4; found, 758.4 Example 15 : Synthesis of GD2-6
Figure 02_image163

依循化合物GD2-3中之合成程序，將1.9克4-甲基二苯胺改換為2.3克N-苯基-2-萘胺，可製備GD2-6成品2.2克，純度99%，產率55%。經昇華純化後得1.7克產物。Following the synthetic procedure in compound GD2-3, replacing 1.9 g of 4-methyldiphenylamine with 2.3 g of N-phenyl-2-naphthylamine, 2.2 g of GD2-6 finished product can be prepared, with a purity of 99% and a yield of 55% . After purification by sublimation, 1.7 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.73(d, 1H), δ8.70(d, 1H) , δ8.20-8.01(m, 5H) , δ7.78(d, 1H), δ7.51-7.28(m, 2H) , δ7.25-7.07(m, 6H),δ7.02-6.87(m, 20H) , δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.73(d, 1H), δ8.70(d, 1H), δ8.20-8.01(m, 5H), δ7.78(d, 1H), δ7. 51-7.28(m, 2H), δ7.25-7.07(m, 6H), δ7.02-6.87(m, 20H), δ1.58(s, 6H).

MS (m/z)：[M +] calcd. C 61H 42N 2for, 802.3；found, 802.3 實施例 16 ： GD2-14 之合成

Figure 02_image165
MS (m/z): [M + ] calcd. C 61 H 42 N 2 for, 802.3; found, 802.3 Example 16 : Synthesis of GD2-14
Figure 02_image165

依循化合物GD2-3中之合成程序，將1.9克4-甲基二苯胺改換為3.0克N-(3,4-二甲基苯基)-4-二苯並呋喃基胺，可製備GD2-14成品2.3克，純度99%，產率49%。經昇華純化後得1.6克產物。Following the synthetic procedure in compound GD2-3, replacing 1.9 g of 4-methyldiphenylamine with 3.0 g of N-(3,4-dimethylphenyl)-4-dibenzofuranylamine can prepare GD2- The finished product of 14 is 2.3 grams, the purity is 99%, and the yield is 49%. After purification by sublimation, 1.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.73(d, 1H), δ8.69(d, 1H) , δ8.29-8.02(m, 5H) , δ7.98-7.86(m, 4H), 7.61-7.38(m, 3H), δ7.36-7.06(m, 13H), δ6.82-6.62(m, 5H) , δ2.29-2.05(m, 12H), δ1.58(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.73(d, 1H), δ8.69(d, 1H), δ8.29-8.02(m, 5H), δ7.98-7.86(m, 4H), 7.61-7.38(m, 3H), δ7.36-7.06(m, 13H), δ6.82-6.62(m, 5H), δ2.29-2.05(m, 12H), δ1.58(s, 6H) .

MS (m/z)：[M +] calcd. C 69H 50N 2O 2for, 938.4；found, 938.3 實施例 17 ： GD3-3 之合成

Figure 02_image167
MS (m/z): [M + ] calcd. C 69 H 50 N 2 O 2 for, 938.4; found, 938.3 Example 17 : Synthesis of GD3-3
Figure 02_image167

在氮氣下於三頸瓶中置入3.3克中間體C3(Intermediate C3)與2.1克4,4'-二甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.7克第三丁醇鉀，0.11克乙酸鈀，0.26克三叔丁基膦，加熱迴流反應2小時，冷卻濃縮後析出固體，固體以四氫呋喃 (THF)再結晶2次，過濾得產物2.8克，純度99%，產率63%。經昇華純化後得2.3克產物。Put 3.3 g of Intermediate C3 (Intermediate C3) and 2.1 g of 4,4'-dimethyldiphenylamine, 40 ml of toluene (Tol) into a three-necked flask under nitrogen, and add 1.7 g of potassium tert-butoxide. 0.11 g of palladium acetate, 0.26 g of tri-tert-butyl phosphine, heated under reflux and reacted for 2 hours. After cooling and concentration, a solid precipitated out. The solid was recrystallized twice with tetrahydrofuran (THF). The product was filtered to obtain 2.8 g with a purity of 99% and a yield of 63%. . After purification by sublimation, 2.3 grams of product were obtained.

1H NMR (400MHz, CDCl 3)：δ8.87(d, 2H), δ8.21-8.02(m, 5H), 7.96(d, 1H), δ7.77(d, 1H), δ7.56(t, 1H), δ7.51-7.33(m, 2H), δ7.25-6.91(m, 26H) , δ2.28(d, 12H). 1 H NMR (400MHz, CDCl 3 ): δ8.87(d, 2H), δ8.21-8.02(m, 5H), 7.96(d, 1H), δ7.77(d, 1H), δ7.56( t, 1H), δ7.51-7.33(m, 2H), δ7.25-6.91(m, 26H), δ2.28(d, 12H).

MS (m/z)：[M +] calcd. C 67H 50N 2for, 882.4；found, 882.4 實施例 18 ： GD4-3 之合成

Figure 02_image169
MS (m/z): [M + ] calcd. C 67 H 50 N 2 for, 882.4; found, 882.4 Example 18 : Synthesis of GD4-3
Figure 02_image169

依循化合物GD3-3中之合成程序，將中間體C3(Intermediate C3)改換中間體C4(Intermediate C4)，可製備GD4-3成品2.1克，純度99%，產率48%。經昇華純化後得1.5克產物。Following the synthetic procedure in compound GD3-3, replacing intermediate C3 (Intermediate C3) with intermediate C4 (Intermediate C4), 2.1 grams of finished product of GD4-3 can be prepared with a purity of 99% and a yield of 48%. After purification by sublimation, 1.5 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.72(d, 1H), δ8.69(d, 1H) , δ8.21-8.02(m, 5H) , δ7.77(d, 1H), δ7.50-7.32(m, 2H), δ7.07-6.89(m, 28H), δ2.27(d, 12H). 1 H NMR (400MHz, CDCl 3 ): δ8.72(d, 1H), δ8.69(d, 1H), δ8.21-8.02(m, 5H), δ7.77(d, 1H), δ7. 50-7.32(m, 2H), δ7.07-6.89(m, 28H), δ2.27(d, 12H).

MS (m/z)：[M +] calcd. C 67H 50N 2for, 882.4；found, 882.4 MS (m/z): [M + ] calcd. C 67 H 50 N 2 for, 882.4; found, 882.4

特別說明的是，雖然上述實施例6-18中介紹了不同的材料及其合成方法，然本發明之材料並不限制於此。根據上述實施例之合成方法製備不同的起始物，再經由Buchwald-hartwig偶聯反應(即[0024]段所述第4步之反應)便可合成出多種不同的成品材料，其組合可如下表1所示：In particular, although different materials and their synthesis methods are described in the foregoing Examples 6-18, the materials of the present invention are not limited thereto. According to the synthesis method of the above embodiment, different starting materials are prepared, and then through the Buchwald-hartwig coupling reaction (ie the reaction in step 4 described in paragraph [0024]), a variety of different finished materials can be synthesized. The combination can be as follows Table 1 shows:

表1  Buchwald-hartwig偶聯反應起始物與產物對照表

Figure 02_image171
二級胺                        中間體C                                                                                        產物 中間體
Figure 02_image173
 中間體C1 中間體C2 中間體C3 中間體C4
Figure 02_image175
 GD1-1 GD2-1 GD3-1 GD4-1
Figure 02_image177
 GD1-2 GD2-2 GD3-2 GD4-2
Figure 02_image179
 GD1-3      
Figure 02_image181
 GD1-4      
Figure 02_image183
 GD1-5 GD2-3 GD3-3 GD4-3
Figure 02_image185
 GD1-6 GD2-4    
Figure 02_image187
 GD1-7      
Figure 02_image189
 GD1-8 GD2-5 GD3-4 GD4-4
Figure 02_image191
 GD1-9            
Figure 02_image193
 GD1-10 GD2-6 GD3-5 GD4-5
Figure 02_image195
   GD2-7 GD3-6 GD4-6
Figure 02_image197
 GD1-11 GD2-8    
Figure 02_image199
 GD1-12      
Figure 02_image201
 GD1-13 GD2-9    
Figure 02_image203
 GD1-14 GD2-10 GD3-7 GD4-7
Figure 02_image205
 GD1-15      
Figure 02_image207
 GD1-16 GD2-11 GD3-8 GD4-8
Figure 02_image209
 GD1-17 GD2-12    
Figure 02_image211
 GD1-18 GD2-13 GD3-9 GD4-9
Figure 02_image213
 GD1-19 GD2-14    
Figure 02_image215
 GD1-20      
Figure 02_image217
 GD1-21 GD2-15    
Figure 02_image219
 GD1-22      
Figure 02_image221
 GD1-23      
Figure 02_image223
 GD1-24       Table 1 Comparison table of starting materials and products of Buchwald-hartwig coupling reaction
Figure 02_image171
Secondary amine intermediate C product Intermediate
Figure 02_image173
 Intermediate C1 Intermediate C2 Intermediate C3 Intermediate C4
Figure 02_image175
 GD1-1 GD2-1 GD3-1 GD4-1
Figure 02_image177
 GD1-2 GD2-2 GD3-2 GD4-2
Figure 02_image179
 GD1-3
Figure 02_image181
 GD1-4
Figure 02_image183
 GD1-5 GD2-3 GD3-3 GD4-3
Figure 02_image185
 GD1-6 GD2-4
Figure 02_image187
 GD1-7
Figure 02_image189
 GD1-8 GD2-5 GD3-4 GD4-4
Figure 02_image191
 GD1-9
Figure 02_image193
 GD1-10 GD2-6 GD3-5 GD4-5
Figure 02_image195
 GD2-7 GD3-6 GD4-6
Figure 02_image197
 GD1-11 GD2-8
Figure 02_image199
 GD1-12
Figure 02_image201
 GD1-13 GD2-9
Figure 02_image203
 GD1-14 GD2-10 GD3-7 GD4-7
Figure 02_image205
 GD1-15
Figure 02_image207
 GD1-16 GD2-11 GD3-8 GD4-8
Figure 02_image209
 GD1-17 GD2-12
Figure 02_image211
 GD1-18 GD2-13 GD3-9 GD4-9
Figure 02_image213
 GD1-19 GD2-14
Figure 02_image215
 GD1-20
Figure 02_image217
 GD1-21 GD2-15
Figure 02_image219
 GD1-22
Figure 02_image221
 GD1-23
Figure 02_image223
 GD1-24

上表中，化學式底下的數字為CAS編號，表示該結構之藥品可於商業市場上購得。根據上表所示，可簡易的經由不同二級胺與中間體C進行Buchwald-hartwig偶聯反應，合成出多種不同的發光材料GD。GD系列材料的發光波長介於500至535 nm之間，屬於綠光發光材料。 實施例 19 ：玻璃轉移溫度 (Tg) 之測量 In the above table, the number under the chemical formula is the CAS number, which means that drugs with this structure are available on the commercial market. According to the above table, a variety of different luminescent materials GD can be synthesized by Buchwald-hartwig coupling reaction via different secondary amines and intermediate C easily. The emission wavelength of GD series materials is between 500 and 535 nm, which is a green light emitting material. Example 19 : Measurement of glass transition temperature (Tg)

上述實施例中合成之發光層客體材料，經由熱示差掃描分析儀(Differential Scanning Calorimetry, DSC)測得玻璃轉移溫度(Tg)，結果列於下表2：The glass transition temperature (Tg) of the light-emitting layer guest material synthesized in the above examples was measured by a differential scanning calorimetry (DSC). The results are listed in Table 2 below:

表2 實施例與比較例材料的Tg(玻璃轉移溫度) 發光客體材料 Tg (℃) GD1-2 162.4 GD1-5 175.8 GD1-8 175.1 GD1-9 180.5 GD1-10 181.7 GD1-12 212.6 GD1-15 191.2 GD1-19 182.3 GD2-3 163.5 GD2-6 172.1 GD2-14 169.5 GD3-3 183.6 GD4-3 171.8 C545T(比較例) ~100 Table 2 Tg (Glass Transition Temperature) of Examples and Comparative Examples Luminescent object material Tg (℃) GD1-2 162.4 GD1-5 175.8 GD1-8 175.1 GD1-9 180.5 GD1-10 181.7 GD1-12 212.6 GD1-15 191.2 GD1-19 182.3 GD2-3 163.5 GD2-6 172.1 GD2-14 169.5 GD3-3 183.6 GD4-3 171.8 C545T (comparative example) ~100

由表2可知，本發明之材料玻璃轉移溫度Tg皆高於160℃，較目前常用之發光層客體材料C545T具有更高的玻璃轉移溫度，熱穩定性較高，適合應用於工業製程。 實施例 20 ：元件測試 It can be seen from Table 2 that the glass transition temperature Tg of the material of the present invention is higher than 160°C, which has a higher glass transition temperature and higher thermal stability than the currently commonly used light-emitting layer guest material C545T, and is suitable for industrial processes. Embodiment 20 : component test

請參考第1圖，其繪示本實施例使用之有機電激發光裝置10的結構。本實施例之有機電激發光裝置10主要是以真空蒸鍍方式製備，包含玻璃基板1、ITO 2(陽極層)、電洞注入層3(hole injection layer, HIL)、電洞傳輸層4(hole transport layer, HTL)、發光層5(主體發光材料與客體發光材料)、電子傳輸層6(electron transport layer, ETL)以及陰極層7。陽極層2和陰極層7係分別與一外部電源接觸形成電通路。本實施例係利用此裝置測試本發明之有機電激發光裝置的特性。Please refer to FIG. 1, which shows the structure of the organic electroluminescence device 10 used in this embodiment. The organic electroluminescence device 10 of this embodiment is mainly prepared by vacuum evaporation, and includes a glass substrate 1, an ITO 2 (anode layer), a hole injection layer 3 (HIL), and a hole transport layer 4 ( hole transport layer (HTL), light-emitting layer 5 (host light-emitting material and guest light-emitting material), electron transport layer 6 (ETL), and cathode layer 7. The anode layer 2 and the cathode layer 7 are respectively in contact with an external power source to form electrical paths. This embodiment uses this device to test the characteristics of the organic electroluminescence device of the present invention.

特別說明的是，實際應用時本發明的有機電激發光裝置並不限於上述態樣，而可以依據需求調整結構。舉例來說，可在電子傳輸層6與陰極層7之間設計一電子注入層(electron injection layer, EIL)，在電子傳輸層和發光層之間設計一電洞阻擋層，或者可以省略電洞注入層3，本發明並不對有機電激發光裝置的結構限制。In particular, in actual application, the organic electroluminescent device of the present invention is not limited to the above aspect, and the structure can be adjusted according to requirements. For example, an electron injection layer (EIL) can be designed between the electron transport layer 6 and the cathode layer 7, and a hole blocking layer can be designed between the electron transport layer and the light emitting layer, or the holes can be omitted. The injection layer 3 does not limit the structure of the organic electroluminescence device in the present invention.

本發明之有機電激發光裝置的特徵在於其發光層之客體材料為本案式(I)化合物GD，另外採用習知綠光客體發光材料C545T當作比較例。除此之外，實施例與比較例之有機電激發光裝置的其他層體所用材料係完全相同，詳列如下表3： 表3 有機激發光裝置之各層材料 結構 材料 基板1 玻璃 陽極層2 銦錫氧化物ITO 電洞注入層(HIL)3 2-TNATA (70nm) 電洞傳輸層(HTL)4 NPB 10nm 發光層5 主體：ADN 客體C545T或GD 3% (30nm) 電子傳輸層(ETL)6 Alq 325nm 陰極層7 LiF 1nm, Al 150nm

Figure 02_image225
Figure 02_image227
Figure 02_image229
Figure 02_image231
Figure 02_image233
The organic electroluminescent device of the present invention is characterized in that the guest material of the luminescent layer is the compound GD of formula (I), and the conventional green guest luminescent material C545T is used as a comparative example. In addition, the materials used in the other layers of the organic electroluminescent device of the embodiment and the comparative example are exactly the same, as detailed in Table 3 below: Table 3 Materials of each layer of the organic electroluminescent device structure material Substrate 1 glass Anode layer 2 Indium tin oxide ITO Hole Injection Layer (HIL) 3 2-TNATA (70nm) Hole Transport Layer (HTL) 4 NPB 10nm Light emitting layer 5 Subject: ADN object C545T or GD 3% (30nm) Electron Transport Layer (ETL) 6 Alq 3 25nm Cathode layer 7 LiF 1nm, Al 150nm
Figure 02_image225
Figure 02_image227
Figure 02_image229
Figure 02_image231
Figure 02_image233

使用本發明實施例之各種材料，以及傳統材料C545T作為發光客體材料的有機電激發光裝置之測試結果如下表4所示： 表4 實施例與比較例之有機電激發光裝置的特性 實施例 Dopant Turn-on (V) EL max(nm) EQE* CE* (cd/A) 1 GD1-2 4.16 512 8.06% 27.3 2 GD1-5 4.39 518 7.60% 26.8 3 GD1-8 4.50 521 8.01% 28.89 4 GD1-10 3.95 512 7.87% 26.7 5 GD1-12 4.38 517 7.75% 27.2 6 GD1-19 4.36 507 8.11% 26.3 7 GD2-3 4.48 519 7.67% 27.5 8 GD2-14 4.41 507 8.03% 26.0 9 GD3-3 4.42 518 7.68% 26.6 10 GD4-3 4.47 519 7.76% 27.3 比較例1 C545T 4.56 522 7.07% 25.8 *在電流密度100 mA/cm 2下的測量值 The test results of the organic electroluminescent device using the various materials of the embodiment of the present invention and the traditional material C545T as the luminescent guest material are shown in Table 4 below: Table 4 Characteristics of the organic electroluminescent device of the embodiment and comparative Example Dopant Turn-on (V) EL max (nm) EQE* CE* (cd/A) 1 GD1-2 4.16 512 8.06% 27.3 2 GD1-5 4.39 518 7.60% 26.8 3 GD1-8 4.50 521 8.01% 28.89 4 GD1-10 3.95 512 7.87% 26.7 5 GD1-12 4.38 517 7.75% 27.2 6 GD1-19 4.36 507 8.11% 26.3 7 GD2-3 4.48 519 7.67% 27.5 8 GD2-14 4.41 507 8.03% 26.0 9 GD3-3 4.42 518 7.68% 26.6 10 GD4-3 4.47 519 7.76% 27.3 Comparative example 1 C545T 4.56 522 7.07% 25.8 *Measured value under current density of 100 mA/cm 2

由表4可知，使用本發明之材料作為發光材料的有機電激發光裝置，較使用傳統發光材料C545T的有機電激發光裝置具有更低的驅動電壓(Turn-on voltage)與較高的發光效率(外部量子效率External Quantum Efficiency, EQE)。例如驅動電壓可降低達13%(GD1-10)，發光效率可提昇達15%(GD1-19)。此外，上述材料的製備方式簡單，易於合成及純化，具有商業化應用之潛力。It can be seen from Table 4 that the organic electroluminescent device using the material of the present invention as the luminescent material has a lower driving voltage (Turn-on voltage) and higher luminous efficiency than the organic electroluminescent device using the traditional luminescent material C545T (External Quantum Efficiency, EQE). For example, the driving voltage can be reduced by up to 13% (GD1-10), and the luminous efficiency can be increased by up to 15% (GD1-19). In addition, the preparation methods of the above-mentioned materials are simple, easy to synthesize and purify, and have the potential for commercial application.

雖然本發明以實施例說明如上，惟此些實施例並非用以限制本發明。本領域之通常知識者在不脫離本發明技藝精神的範疇內，當可對此些實施例進行等效實施或變更，故本發明的保護範圍應以其後所附之申請專利範圍為準。Although the present invention is described above with examples, these examples are not intended to limit the present invention. Those skilled in the art can make equivalent implementations or changes to these embodiments without departing from the technical spirit of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of the patent application attached thereafter.

1:玻璃基板 10:有機電激發光裝置 2:ITO(陽極層) 3:電洞注入層 4:電洞傳輸層 5:發光層 6:電子傳輸層 7:陰極層1: glass substrate 10: Organic electroluminescence device 2: ITO (anode layer) 3: hole injection layer 4: hole transport layer 5: Light-emitting layer 6: Electron transport layer 7: Cathode layer

第1圖為本發明之有機電激發光裝置的示意圖。Figure 1 is a schematic diagram of the organic electroluminescence device of the present invention.

Figure 01_image001
Figure 01_image001

1:玻璃基板 1: glass substrate

10:有機電激發光裝置 10: Organic electroluminescence device

2:ITO(陽極層) 2: ITO (anode layer)

3:電洞注入層 3: hole injection layer

4:電洞傳輸層 4: hole transport layer

5:發光層 5: Light-emitting layer

6:電子傳輸層 6: Electron transport layer

7:陰極層 7: Cathode layer

Claims (10)

一種有機電激發光裝置之材料，係具有下列化學式(I)所示之結構：
Figure 03_image001
(I)； 其中，Ar 1與Ar 2各自獨立為經取代的C 6至C 18芳基、未取代的C 6至C 18芳基、經取代的含有氧原子之雜芳基或未取代的含有氧原子之雜芳基，R各自獨立為C 1至C 4烷基、經取代的C 6至C 12芳基或未取代的C 6至C 12芳基。 A material for an organic electroluminescence device, which has the structure shown in the following chemical formula (I):
Figure 03_image001
(I); wherein Ar 1 and Ar 2 are each independently a substituted C 6 to C 18 aryl group, an unsubstituted C 6 to C 18 aryl group, a substituted oxygen atom-containing heteroaryl group, or an unsubstituted In the heteroaryl group containing an oxygen atom, R is each independently a C 1 to C 4 alkyl group, a substituted C 6 to C 12 aryl group, or an unsubstituted C 6 to C 12 aryl group. 如申請專利範圍第1項所述之材料，其中Ar 1與Ar 2各自獨立為經取代或未取代的
Figure 03_image003
、
Figure 03_image005
或
Figure 03_image007
，且A各自獨立為H、C 1至C 4的烷基或苯。 The material described in item 1 of the scope of patent application, wherein Ar 1 and Ar 2 are each independently substituted or unsubstituted
Figure 03_image003
,
Figure 03_image005
or
Figure 03_image007
, And A is each independently H, a C 1 to C 4 alkyl group, or benzene. 如申請專利範圍第1項所述之材料，其具有下列化學式中任一者所述之結構：
Figure 03_image009
Figure 03_image011
Figure 03_image013
 GD1-1 GD1-2 GD1-3      
Figure 03_image015
Figure 03_image017
Figure 03_image019
 GD1-4 GD1-5 GD1-6      
Figure 03_image021
Figure 03_image023
Figure 03_image025
 GD1-7 GD1-8 GD1-9      
Figure 03_image027
Figure 03_image029
Figure 03_image031
 GD1-10 GD1-11 GD1-12      
Figure 03_image033
Figure 03_image035
Figure 03_image037
 GD1-13 GD1-14 GD1-15      
Figure 03_image039
Figure 03_image041
Figure 03_image043
 GD1-16 GD1-17 GD1-18      
Figure 03_image045
Figure 03_image047
Figure 03_image049
 GD1-19 GD1-20 GD1-21      
Figure 03_image051
Figure 03_image053
Figure 03_image055
 GD1-22 GD1-23 GD1-24      
Figure 03_image057
Figure 03_image059
Figure 03_image061
 GD2-1 GD2-2 GD2-3      
Figure 03_image063
Figure 03_image065
Figure 03_image067
 GD2-4 GD2-5 GD2-6      
Figure 03_image069
Figure 03_image071
Figure 03_image073
 GD2-7 GD2-8 GD2-9      
Figure 03_image075
Figure 03_image077
Figure 03_image079
 GD2-10 GD2-11 GD2-12      
Figure 03_image081
Figure 03_image083
Figure 03_image085
 GD2-13 GD2-14 GD2-15      
Figure 03_image087
Figure 03_image089
Figure 03_image091
 GD3-1 GD3-2 GD3-3      
Figure 03_image093
Figure 03_image095
Figure 03_image097
 GD3-4 GD3-5 GD3-6      
Figure 03_image099
Figure 03_image101
Figure 03_image103
 GD3-7 GD3-8 GD3-9      
Figure 03_image105
Figure 03_image107
Figure 03_image109
 GD4-1 GD4-2 GD4-3      
Figure 03_image111
Figure 03_image113
Figure 03_image115
 GD4-4 GD4-5 GD4-6      
Figure 03_image117
Figure 03_image119
Figure 03_image121
 GD4-7 GD4-8 GD4-9               。
The material described in item 1 of the scope of patent application has a structure described in any of the following chemical formulas:
Figure 03_image009
Figure 03_image011
Figure 03_image013
 GD1-1 GD1-2 GD1-3
Figure 03_image015
Figure 03_image017
Figure 03_image019
 GD1-4 GD1-5 GD1-6
Figure 03_image021
Figure 03_image023
Figure 03_image025
 GD1-7 GD1-8 GD1-9
Figure 03_image027
Figure 03_image029
Figure 03_image031
 GD1-10 GD1-11 GD1-12
Figure 03_image033
Figure 03_image035
Figure 03_image037
 GD1-13 GD1-14 GD1-15
Figure 03_image039
Figure 03_image041
Figure 03_image043
 GD1-16 GD1-17 GD1-18
Figure 03_image045
Figure 03_image047
Figure 03_image049
 GD1-19 GD1-20 GD1-21
Figure 03_image051
Figure 03_image053
Figure 03_image055
 GD1-22 GD1-23 GD1-24
Figure 03_image057
Figure 03_image059
Figure 03_image061
 GD2-1 GD2-2 GD2-3
Figure 03_image063
Figure 03_image065
Figure 03_image067
 GD2-4 GD2-5 GD2-6
Figure 03_image069
Figure 03_image071
Figure 03_image073
 GD2-7 GD2-8 GD2-9
Figure 03_image075
Figure 03_image077
Figure 03_image079
 GD2-10 GD2-11 GD2-12
Figure 03_image081
Figure 03_image083
Figure 03_image085
 GD2-13 GD2-14 GD2-15
Figure 03_image087
Figure 03_image089
Figure 03_image091
 GD3-1 GD3-2 GD3-3
Figure 03_image093
Figure 03_image095
Figure 03_image097
 GD3-4 GD3-5 GD3-6
Figure 03_image099
Figure 03_image101
Figure 03_image103
 GD3-7 GD3-8 GD3-9
Figure 03_image105
Figure 03_image107
Figure 03_image109
 GD4-1 GD4-2 GD4-3
Figure 03_image111
Figure 03_image113
Figure 03_image115
 GD4-4 GD4-5 GD4-6
Figure 03_image117
Figure 03_image119
Figure 03_image121
 GD4-7 GD4-8 GD4-9.
如申請專利範圍第1項所述之材料，其中該材料之發光波長介於500至535 nm。The material described in item 1 of the scope of patent application, wherein the emission wavelength of the material is between 500 to 535 nm. 如申請專利範圍第1至4項中任一項所述之材料，其係作為有機電激發光裝置之發光客體。The material described in any one of items 1 to 4 in the scope of the patent application is used as a light-emitting object of an organic electroluminescence device. 一種有機電激發光裝置，其係包含依以下順序排列之層狀結構：透明基板、陽極層、電洞傳輸層、發光層、電子傳輸層及陰極層； 該有機電激發光裝置之特徵在於該發光層中包含申請專利範圍第1至4項中任一項所述之材料。 An organic electroluminescence device, which comprises a layered structure arranged in the following order: a transparent substrate, an anode layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode layer; The organic electroluminescence device is characterized in that the light-emitting layer contains the material described in any one of items 1 to 4 in the scope of patent application. 如申請專利範圍第6項所述之裝置，其中該陽極層和該電洞傳輸層之間係進一步包含一電洞注入層。According to the device described in claim 6, wherein the anode layer and the hole transport layer further include a hole injection layer. 如申請專利範圍第6項所述之裝置，其中該電子傳輸層和該陰極層之間係進一步包含一電子注入層。According to the device described in item 6 of the scope of patent application, an electron injection layer is further included between the electron transport layer and the cathode layer. 如申請專利範圍第6項所述之裝置，其中該電子傳輸層和該發光層之間係進一步包含一電洞阻擋層。According to the device described in item 6 of the scope of patent application, a hole blocking layer is further included between the electron transport layer and the light-emitting layer. 如申請專利範圍第6項所述之裝置，其中該陽極層和該陰極層係分別與一外部電源接觸形成電通路。The device described in item 6 of the scope of patent application, wherein the anode layer and the cathode layer are respectively in contact with an external power source to form an electrical path.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200541394A (en) * 2004-04-15 2005-12-16 Idemitsu Kosan Co Organic electroluminescent device
US20110084256A1 (en) * 2009-10-09 2011-04-14 Samsung Mobile Display Co., Ltd. Condensed-cyclic compound and organic light emitting diode including organic layer containing the condensed-cyclic compound
US20130126857A1 (en) * 2010-08-03 2013-05-23 Canon Kabushiki Kaisha Novel organic compound and organic light-emitting device including same
TW201321340A (en) * 2011-11-25 2013-06-01 Jnc Corp Benzofluorene compound, material for luminescent layer using the compound, and organic electroluminescent device
CN108342191A (en) * 2017-01-23 2018-07-31 上海和辉光电有限公司 A kind of organic electroluminescent compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200541394A (en) * 2004-04-15 2005-12-16 Idemitsu Kosan Co Organic electroluminescent device
US20110084256A1 (en) * 2009-10-09 2011-04-14 Samsung Mobile Display Co., Ltd. Condensed-cyclic compound and organic light emitting diode including organic layer containing the condensed-cyclic compound
US20130126857A1 (en) * 2010-08-03 2013-05-23 Canon Kabushiki Kaisha Novel organic compound and organic light-emitting device including same
TW201321340A (en) * 2011-11-25 2013-06-01 Jnc Corp Benzofluorene compound, material for luminescent layer using the compound, and organic electroluminescent device
CN108342191A (en) * 2017-01-23 2018-07-31 上海和辉光电有限公司 A kind of organic electroluminescent compounds

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