TWI727889B - Organic electroluminescent devices and material thereof - Google Patents

Organic electroluminescent devices and material thereof Download PDF

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TWI727889B
TWI727889B TW109131935A TW109131935A TWI727889B TW I727889 B TWI727889 B TW I727889B TW 109131935 A TW109131935 A TW 109131935A TW 109131935 A TW109131935 A TW 109131935A TW I727889 B TWI727889 B TW I727889B
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organic electroluminescence
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TW202212320A (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 C 6to C 18aromatic group, or a substituted or unsubstituted heteroaryl group with O atom; each R is individually a C 1to C 4alkyl, or a substituted or unsubstituted C 6to C 12aromatic group. Both R could be connected with a single bond if both are phenyl group.

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 refers 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 (organic) with light-emitting characteristics. 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 Dopant light-emitting materials, mixed into a single host (Host) light-emitting material, so that the device presents different colors.

目前市面上已有如四苯基芘-1,6-二胺(tetraphenylpyrene-1,6-diamine, CAS No.: 76656-53-6，玻璃轉移溫度Tg≒120℃)之類的藍色客體材料，但其有熱穩定性低、壽命短和發光效率低的問題。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。There are already blue guest materials such as tetraphenylpyrene-1,6-diamine (CAS No.: 76656-53-6, glass transition temperature Tg≒120℃) on the market , But it has the problems of low thermal stability, 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、經取代的苯基或未取代的苯基，其中當兩個R皆為苯基時，兩苯基間可以單鍵連結。 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 phenyl group or an unsubstituted phenyl group, wherein when both R groups are both phenyl groups, the two phenyl groups may be connected by a single bond.

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
 BD1-1 BD1-2 BD1-3
Figure 02_image015
Figure 02_image017
Figure 02_image019
 BD1-4 BD1-5 BD1-6
Figure 02_image021
Figure 02_image023
Figure 02_image025
 BD1-7 BD1-8 BD1-9
Figure 02_image027
Figure 02_image029
Figure 02_image031
 BD1-10 BD1-11 BD1-12
Figure 02_image033
Figure 02_image035
Figure 02_image037
 BD1-13 BD1-14 BD1-15
Figure 02_image039
Figure 02_image041
Figure 02_image043
 BD1-16 BD1-17 BD1-18
Figure 02_image045
Figure 02_image047
Figure 02_image049
 BD1-19 BD1-20 BD1-21
Figure 02_image051
Figure 02_image053
Figure 02_image055
 BD2-1 BD2-2 BD2-3
Figure 02_image057
Figure 02_image059
Figure 02_image061
 BD2-4 BD2-5 BD2-6
Figure 02_image063
Figure 02_image065
Figure 02_image067
 BD2-7 BD2-8 BD2-9
Figure 02_image069
Figure 02_image071
Figure 02_image073
 BD3-1 BD3-2 BD3-3
Figure 02_image075
Figure 02_image077
Figure 02_image079
 BD3-4 BD3-5 BD3-6
Figure 02_image081
Figure 02_image083
Figure 02_image085
 BD3-7 BD3-8 BD3-9
Figure 02_image087
Figure 02_image089
Figure 02_image091
 BD3-10 BD3-11 BD3-12
Figure 02_image093
Figure 02_image095
Figure 02_image097
 BD3-13 BD3-14 BD3-15
Figure 02_image099
Figure 02_image101
 及
Figure 02_image103
。 BD3-16 BD3-17 BD3-18 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
 BD1-1 BD1-2 BD1-3
Figure 02_image015
Figure 02_image017
Figure 02_image019
 BD1-4 BD1-5 BD1-6
Figure 02_image021
Figure 02_image023
Figure 02_image025
 BD1-7 BD1-8 BD1-9
Figure 02_image027
Figure 02_image029
Figure 02_image031
 BD1-10 BD1-11 BD1-12
Figure 02_image033
Figure 02_image035
Figure 02_image037
 BD1-13 BD1-14 BD1-15
Figure 02_image039
Figure 02_image041
Figure 02_image043
 BD1-16 BD1-17 BD1-18
Figure 02_image045
Figure 02_image047
Figure 02_image049
 BD1-19 BD1-20 BD1-21
Figure 02_image051
Figure 02_image053
Figure 02_image055
 BD2-1 BD2-2 BD2-3
Figure 02_image057
Figure 02_image059
Figure 02_image061
 BD2-4 BD2-5 BD2-6
Figure 02_image063
Figure 02_image065
Figure 02_image067
 BD2-7 BD2-8 BD2-9
Figure 02_image069
Figure 02_image071
Figure 02_image073
 BD3-1 BD3-2 BD3-3
Figure 02_image075
Figure 02_image077
Figure 02_image079
 BD3-4 BD3-5 BD3-6
Figure 02_image081
Figure 02_image083
Figure 02_image085
 BD3-7 BD3-8 BD3-9
Figure 02_image087
Figure 02_image089
Figure 02_image091
 BD3-10 BD3-11 BD3-12
Figure 02_image093
Figure 02_image095
Figure 02_image097
 BD3-13 BD3-14 BD3-15
Figure 02_image099
Figure 02_image101
 and
Figure 02_image103
. BD3-16 BD3-17 BD3-18

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 electroluminescence 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，上述發光層之發光波長介於450至490 nm。In one embodiment, the emission wavelength of the above-mentioned light-emitting layer is between 450 and 490 nm.

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, an electron injection layer is further included between the electron transport layer and the cathode 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 light-emitting 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、經取代的苯基或未取代的苯基，其中當兩個R皆為苯基時，兩苯基間可以單鍵連結。 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 phenyl group or an unsubstituted phenyl group, wherein when both R groups are both phenyl groups, the two phenyl groups may be connected by a single bond.

當兩個R皆為苯基且兩苯基間以單鍵連結時，所述材料具有如下化學式(II)：

Figure 02_image105
(II) When both Rs are phenyl groups and the two phenyl groups are connected by a single bond, the material has the following chemical formula (II):
Figure 02_image105
(II)

其中Ar 1及Ar 2的定義與式(I)相同。 The definitions of Ar 1 and Ar 2 are the same as those of formula (I).

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_image107
，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 substituted or unsubstituted independently
Figure 02_image003
,
Figure 02_image005
or
Figure 02_image107
, 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 may 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 1或Ar 2之結構中，以波浪線﹏標示的鍵結，表示Ar 1或Ar 2與N的連結位置。而插入環中心的鍵結，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_image109
4個位置其中之一(左右對稱)，而
Figure 02_image107
表示N可鍵結
Figure 02_image111
在4個位置其中之一。 In the structure of Ar 1 or Ar 2 , the bond marked with a wavy line ﹏ indicates the connection position of Ar 1 or Ar 2 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_image109
One of 4 positions (symmetrical left and right), and
Figure 02_image107
Represents N bondable
Figure 02_image111
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_image113
第 2 步：合環反應
Figure 02_image115
(若R-R為以單鍵連接之苯環)
Figure 02_image117
第 3 步：溴化反應
Figure 02_image119
第 4 步： Buchwald-hartwig Coupling 偶聯反應
Figure 02_image121
The material of formula (I) can be obtained, for example, by the following synthesis method: Step 1 : Suzuki coupling reaction
Figure 02_image113
Step 2 : Closing reaction
Figure 02_image115
(If RR is a benzene ring connected by a single bond)
Figure 02_image117
Step 3 : Bromination reaction
Figure 02_image119
Step 4 : Buchwald-hartwig Coupling coupling reaction
Figure 02_image121

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 synthesis methods are all common organic synthesis reactions in industrial applications. The above-mentioned reaction is used for synthesis, the reaction time is short, the preparation is easy, and the by-products are less generated, and the purification difficulty is relatively 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_image123
Hereinafter, several application examples are used to illustrate each step of the above reaction. However, it should be paid special attention 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_image123

2L三頸瓶置入81克9,9-螺二芴-2-硼酸、53克1-溴-2-萘甲酸甲酯，與45克第三丁醇鉀(Potassium tert-butoxide)，置於氮氣系統下，加入900毫升甲苯(Tol)/ 300毫升去離子水，攪拌溶解後再加入5克四(三苯基膦)鈀 (Tetrakis(triphenylphosphine)palladium(0))，加熱迴流反應3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，濃縮後的膠體使用甲苯進行再結晶，過濾得白色固體，烘乾得中間體A成品82 克，產率81%Place 81 grams of 9,9-spirobifluorene-2-boronic acid, 53 grams of methyl 1-bromo-2-naphthoate, and 45 grams of Potassium tert-butoxide in a 2L three-necked flask. Under nitrogen system, add 900ml of toluene (Tol)/300ml of deionized water, stir to dissolve and then add 5g of Tetrakis(triphenylphosphine)palladium(0), heat and reflux for 3 hours. After cooling, the organic layer was separated, and the water layer was extracted twice with 150 ml of toluene. The organic layers were combined and concentrated. The concentrated colloid was recrystallized with toluene, filtered to obtain a white solid, and dried to obtain 82 grams of intermediate A finished product. Rate 81%

本步驟為[0026]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_image125
This step is the first step described in paragraph [0026]: Suzuki coupling reaction. Example 2 : Synthesis of Intermediate B1 (Intermediate B1)
Figure 02_image125

1L三頸瓶置入65克中間體 A，置於氮氣系統下，加入900毫升四氫呋喃(THF)，攪拌溶解後降溫至-85℃，滴入205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400毫升醋酸與40毫升鹽酸，加熱迴流1hr，冷卻後加入甲醇，固體析出後進行過濾，濾餅使用水與甲醇沖洗2次，收集固體使用甲苯進行再結晶2次，過濾收得白色固體，烘乾得中間體 B1成品 50克，產率80%。Put 65 grams of Intermediate A in a 1L three-necked flask, place it under a nitrogen system, add 900 ml of tetrahydrofuran (THF), stir to dissolve and then cool to -85°C, drop in 205 ml of 1.6M methyllithium (Methyllithium), and stir for 30 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 400 ml of acetic acid and 40 ml of hydrochloric acid, heat to reflux for 1 hr, add methanol after cooling, and proceed after solid precipitation. After filtering, the filter cake was washed twice with water and methanol, the solid was collected and recrystallized twice with toluene, the white solid was collected by filtration, and dried to obtain 50 g of intermediate B1 finished product, with a yield rate of 80%.

本步驟為[0026]段所述之第2步：合環反應。 實施例 3 ：中間體 C1 (Intermediate C1) 之合成

Figure 02_image127
This step is the second step described in paragraph [0026]: ring closure reaction. Example 3 : Synthesis of Intermediate C1 (Intermediate C1)
Figure 02_image127

1L 三頸瓶置入31克中間體 B1，置於氮氣系統下，加入500毫升1,2-二氯乙烷(DCE)攪拌溶解，加入23克溴水(Br 2)室溫下攪拌20分鐘，再加熱至迴流反應1小時，加入200ml 1N KOH水溶液中止反應，使用1,2-二氯乙烷(DCE)進行萃取，收集有機層並濃縮，濃縮後的膠體使用甲苯進行再結晶2次，過濾得淡黃色固體，烘乾得中間體C1產物38克，產率93%。 Put 31 g of Intermediate B1 in a 1L three-necked flask, place it under a nitrogen system, add 500 ml of 1,2-dichloroethane (DCE) and stir to dissolve, add 23 g of bromine water (Br 2 ) and stir at room temperature for 20 minutes , And then heated to reflux for 1 hour, add 200ml of 1N KOH aqueous solution to stop the reaction, use 1,2-dichloroethane (DCE) for extraction, collect the organic layer and concentrate, the concentrated colloid is recrystallized twice with toluene, A light yellow solid was obtained by filtration and dried to obtain 38 g of intermediate C1 product with a yield of 93%.

本步驟為[0026]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_image129
This step is the third step described in paragraph [0026]: bromination reaction. Example 4 : Synthesis of Intermediate B2 (Intermediate B2)
Figure 02_image129

0.5L三頸瓶置入32克中間體 A，置於氮氣系統下，加入450毫升四氫呋喃(THF)，攪拌溶解後降溫至-85℃，滴入84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，固體析出後進行過濾，濾餅使用水與甲醇沖洗2次，收集固體使用甲苯進行再結晶2次，過濾收得白色固體，烘乾得中間體 B2成品22 克，產率74%。Put 32 g of intermediate A in a 0.5L three-necked flask, place it under a nitrogen system, add 450 ml of tetrahydrofuran (THF), stir to dissolve and then cool to -85°C, drop in 84 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, use ethyl acetate to extract, collect and concentrate the organic layer, add 200 ml of acetic acid and 20 ml of hydrochloric acid, heat to reflux for 1 hour, add methanol after cooling, and solid precipitate After filtering, the filter cake was washed twice with water and methanol, the solid was collected and recrystallized twice with toluene, the white solid was collected by filtration, and dried to obtain 22 g of intermediate B2 finished product, with a yield of 74%.

本步驟為[0026]段所述之第2步：合環反應。 實施例 5 ：中間體 C2 (Intermediate C2) 之合成

Figure 02_image131
This step is the second step described in paragraph [0026]: ring closure reaction. Example 5 : Synthesis of Intermediate C2
Figure 02_image131

1L 三頸瓶置入18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14克溴水(Br 2)室溫下攪拌20分鐘，再加熱至迴流反應1小時，加入150ml 1N KOH水溶液中止反應，使用1,2-二氯乙烷(DCE)進行萃取，收集有機層並濃縮，濃縮後的膠體使用甲苯進行再結晶2次，過濾得淡黃色固體，烘乾得中間體C2產物21克，產率90%。 Put 18 grams 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 14 grams of bromine water (Br 2 ) and stir at room temperature for 20 minutes , And then heated to reflux for 1 hour, add 150ml of 1N KOH aqueous solution to stop the reaction, use 1,2-dichloroethane (DCE) for extraction, collect the organic layer and concentrate, and use toluene to recrystallize the concentrated colloid twice. A light yellow solid was obtained by filtration and dried to obtain 21 g of intermediate C2 product with a yield of 90%.

本步驟為[0026]段所述之第3步：溴化反應。 實施例 6 ： 中間體 B3-1 (Intermediate B3-1) 之合成

Figure 02_image133
This step is the third step described in paragraph [0026]: bromination reaction. Example 6 : Synthesis of Intermediate B3-1 (Intermediate B3-1)
Figure 02_image133

1L三頸瓶置入40克中間體 A，置於氮氣系統下，加入400毫升甲苯(Tol)，攪拌溶解後冰浴降溫，慢慢倒入30毫升濃硫酸，室溫攪拌20分鐘，加熱迴流反應24小時，反應完降溫並加水中止反應，攪拌過濾收固體，濾餅使用水與甲醇沖洗2次，收集固體使用四氫呋喃與甲醇混合溶劑再結晶1次，過濾收得紅色固體，烘乾得中間體 B3-1成品 31克，產率83%。 實施例 7 ： 中間體 B3 (Intermediate B3) 之合成

Figure 02_image135
Put 40 g of Intermediate A in a 1L three-necked flask, place it under a nitrogen system, add 400 ml of toluene (Tol), stir to dissolve and cool in an ice bath, slowly pour 30 ml of concentrated sulfuric acid, stir at room temperature for 20 minutes, and heat to reflux React for 24 hours. After the reaction, cool down and add water to stop the reaction. Stir and filter to collect solids. The filter cake is washed twice with water and methanol. The solids are collected and recrystallized once with a mixed solvent of tetrahydrofuran and methanol. The red solids are collected by filtration. The finished product of body B3-1 is 31 grams, and the yield is 83%. Intermediate B3 (Intermediate B3) of Synthesis: Example 7
Figure 02_image135

0.5L三頸瓶置入23.2克2-溴聯苯，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45毫升2.5M正丁基鋰(n-Butyllithium)，攪拌1小時，將23.4克中間體B3-1固體加入反應瓶中，移除低溫槽後攪拌16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，固體析出後進行過濾，濾餅使用水與甲醇沖洗2次，收集固體使用甲苯進行再結晶2次，過濾收得白色固體，烘乾得中間體 B3成品21 克，產率70%。Put 23.2 g of 2-bromobiphenyl in a 0.5L three-necked flask, place it under a nitrogen system, add 400 ml of tetrahydrofuran (THF), stir to dissolve and then cool to -85℃, drop 45 ml of 2.5M n-butyl lithium (n -Butyllithium), stir for 1 hour, add 23.4 g of intermediate B3-1 solid into the reaction flask, remove the low temperature tank and stir for 16 hours, add 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 were heated and refluxed for 1 hr. After cooling, methanol was added. The solid was separated out and filtered. The filter cake was washed twice with water and methanol. The solid was collected and recrystallized with toluene twice. The white solid was collected by filtration and dried. 21 grams of finished product of intermediate B3 was dried, and the yield was 70%.

實施例6及7為另外一種合環反應（[0026]段所述之第2步）。 實施例 8 ：中間體 C3 (Intermediate C3) 之合成

Figure 02_image137
Examples 6 and 7 are another ring closure reaction (Step 2 described in paragraph [0026]). Intermediate C3 (Intermediate C3) of Synthesis: Example 8
Figure 02_image137

1L 三頸瓶置入12.1克中間體 B3，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9.6克溴水(Br 2)室溫下攪拌20分鐘，再加熱至迴流反應2小時，冷卻後加入甲醇，析出固體進行過濾，濾餅使用水與甲醇沖洗2次，收集固體使用四氫呋喃進行再結晶2次，過濾得白色固體，烘乾得中間體C3產物13.4克，產率88%。 Put 12.1 g of Intermediate B3 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 9.6 g of bromine water (Br 2 ) and stir at room temperature for 20 minutes , And then heated to reflux for 2 hours. After cooling, add methanol to precipitate solids and filter. The filter cake is washed twice with water and methanol. The solids are collected and recrystallized twice with tetrahydrofuran. A white solid is obtained by filtration and dried to obtain intermediate C3. The product was 13.4 g, and the yield was 88%.

本步驟為[0026]段所述之第3步：溴化反應。 實施例 9 ： BD1-2 之合成

Figure 02_image139
This step is the third step described in paragraph [0026]: bromination reaction. Example 9 : Synthesis of BD1-2
Figure 02_image139

在氮氣下於三頸瓶中置入2.6克中間體C1(Intermediate C1)與1.5克4-甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.3克第三丁醇鉀，0.09克乙酸鈀，0.21克三第三丁基膦，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/甲醇(THF/MTA)再結晶2次，過濾得產物2.2克，純度99%，產率65%。經昇華純化後得1.7克產物。Under nitrogen, put 2.6 g of Intermediate C1 (Intermediate C1), 1.5 g of 4-methyldiphenylamine, 40 ml of toluene (Tol) into a three-necked flask, stir to dissolve, add 1.3 g of potassium tert-butoxide, and 0.09 g of palladium acetate , 0.21 g of tri-tertiary butyl phosphine, heated at reflux for 2 hours, cooled and concentrated to precipitate a solid, the solid was recrystallized twice with tetrahydrofuran/methanol (THF/MTA), filtered to obtain 2.2 g of the product, purity 99%, yield 65 %. After purification by sublimation, 1.7 g of product was obtained.

本步驟為[0026]段所述之第4步：Buchwald-hartwig 偶聯反應，產物BD1-2之NMR圖譜及質譜檢測結果如下：This step is the fourth step described in paragraph [0026]: Buchwald-hartwig coupling reaction. The NMR spectrum and mass spectrometry results of the product BD1-2 are as follows:

1H NMR (400MHz, CDCl 3)：δ8.23(d, 1H), δ7.95(d, 1H), δ7.83(d, 3H), δ7.69(d, 1H), δ7.50(s, 1H), δ7.39(s, 1H) , δ7.34(t, 3H) ,δ7.28-6.79(m, 24H) ,δ6.51(s, 1H) , δ2.25(s, 6H) , δ1.53(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.23(d, 1H), δ7.95(d, 1H), δ7.83(d, 3H), δ7.69(d, 1H), δ7.50( s, 1H), δ7.39(s, 1H), δ7.34(t, 3H) ,δ7.28-6.79(m, 24H) ,δ6.51(s, 1H), δ2.25(s, 6H ), δ1.53(s, 6H).

MS (m/z)：[M +] calcd. C64H48N2 for, 844；found,844 實施例 10 ： BD1-3 之合成

Figure 02_image141
MS (m/z): [M + ] calcd. C64H48N2 for, 844; found, 844 Example 10 : Synthesis of BD1-3
Figure 02_image141

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為1.7克4,4'-二甲基二苯胺，可製備 BD1-3成品2.4克，純度99%，收率70%。經昇華純化後得1.8克產物。 Following the synthetic procedure in compound BD1-2 , 1.5 g of 4-methyldiphenylamine was changed to 1.7 g of 4,4'-dimethyldiphenylamine, 2.4 g of BD1-3 finished product can be prepared, with a purity of 99% and a yield of 70 %. 1.8 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.21(d, 1H), δ7.93(d, 1H), δ7.82(d, 3H), δ7.67(d, 1H), δ7.48(s, 1H), δ7.40-7.08(m, 8H) , δ7.01-6.65(m, 18H) , δ6.51(s, 1H), δ2.24(s, 12H), δ1.54(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.21(d, 1H), δ7.93(d, 1H), δ7.82(d, 3H), δ7.67(d, 1H), δ7.48( s, 1H), δ7.40-7.08(m, 8H), δ7.01-6.65(m, 18H), δ6.51(s, 1H), δ2.24(s, 12H), δ1.54(s , 6H).

MS (m/z)：[M +] calcd. C66H52N2 for, 872；found,872 實施例 11 ： BD1-4 之合成

Figure 02_image143
MS (m/z): [M + ] calcd. C66H52N2 for, 872; found, 872 Example 11 : Synthesis of BD1-4
Figure 02_image143

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為1.7克3,3'-二甲基二苯胺，可製備 BD1-4成品2.4克，純度99%，收率74%。經昇華純化後得2.0克產物。 Following the synthetic procedure in compound BD1-2 , changing 1.5 g of 4-methyldiphenylamine to 1.7 g of 3,3'-dimethyldiphenylamine, 2.4 g of BD1-4 product can be prepared with a purity of 99% and a yield of 74 %. After purification by sublimation, 2.0 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.25(d, 1H), δ7.95(d, 1H), δ7.83(d, 3H), δ7.71(d, 1H), δ7.54(s, 1H), δ7.41(s, 1H) , δ7.35(t, 3H) , δ7.28-7.21(m, 1H) , δ7.17-6.87(m, 10H) , δ6.85-6.68(m, 11H), δ6.55(s, 1H), δ2.16(s, 6H), δ2.12(s, 6H), δ1.55(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.25(d, 1H), δ7.95(d, 1H), δ7.83(d, 3H), δ7.71(d, 1H), δ7.54( s, 1H), δ7.41(s, 1H), δ7.35(t, 3H), δ7.28-7.21(m, 1H), δ7.17-6.87(m, 10H), δ6.85-6.68 (m, 11H), δ6.55(s, 1H), δ2.16(s, 6H), δ2.12(s, 6H), δ1.55(s, 6H).

MS (m/z)：[M +] calcd. C66H52N2 for, 872；found,872 實施例 12 ： BD1-7 之合成

Figure 02_image145
MS (m/z): [M + ] calcd. C66H52N2 for, 872; found, 872 Example 12 : Synthesis of BD1-7
Figure 02_image145

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為1.8克N-苯基-2-萘胺，可製備 BD1-7成品2.1克，純度99%，收率60%。經昇華純化後得1.7克產物。 Following the synthetic procedure in compound BD1-2 , changing 1.5 g of 4-methyldiphenylamine to 1.8 g of N-phenyl-2-naphthylamine, 2.1 g of finished product of BD1-7 can be prepared with a purity of 99% and a yield of 60% . After purification by sublimation, 1.7 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.27(d, 1H), δ7.98(d, 1H) , δ7.86(s, 1H) , δ7.79(d, 2H), δ7.75(d, 1H), δ7.72-7.53(m, 5H), δ7.50-7.25(m, 14H) , δ7.23-6.91(m, 16H) , δ6.58(s, 1H) , δ1.55(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.27(d, 1H), δ7.98(d, 1H), δ7.86(s, 1H), δ7.79(d, 2H), δ7.75( d, 1H), δ7.72-7.53(m, 5H), δ7.50-7.25(m, 14H), δ7.23-6.91(m, 16H), δ6.58(s, 1H), δ1.55 (s, 6H).

MS (m/z)：[M +] calcd. C70H48N2 for, 916；found, 916 實施例 13 ： GD1-13 之合成

Figure 02_image147
MS (m/z): [M + ] calcd. C70H48N2 for, 916; found, 916 Example 13 : Synthesis of GD1-13
Figure 02_image147

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為2.2克N-苯基-4-二苯並呋喃基胺，可製備 BD1-13成品2.0克，純度99%，收率50%。經昇華純化後得1.4克產物。 Following the synthetic procedure in compound BD1-2 , changing 1.5 g of 4-methyldiphenylamine to 2.2 g of N-phenyl-4-dibenzofuranylamine, 2.0 g of BD1-13 product can be prepared with a purity of 99%. The yield is 50%. 1.4 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.25(d, 1H), δ8.06(d, 1H) , δ7.92(d, 1H) , δ7.90-7.84(m, 2H), δ7.76-7.58(m, 5H), δ7.57(s, 1H), δ7.52(s, 1H) , δ7.40-7.17(m, 10H) , δ7.16-7.04(m, 9H) , δ7.00-6.75(m, 10H) , δ6.46(d, 1H), δ1.54(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.25(d, 1H), δ8.06(d, 1H), δ7.92(d, 1H), δ7.90-7.84(m, 2H), δ7. 76-7.58(m, 5H), δ7.57(s, 1H), δ7.52(s, 1H), δ7.40-7.17(m, 10H), δ7.16-7.04(m, 9H), δ7 .00-6.75(m, 10H), δ6.46(d, 1H), δ1.54(s, 6H).

MS (m/z)：[M +] calcd. C74H48N2O2 for, 996；found, 996 實施例 14 ： BD1-14 之合成

Figure 02_image149
MS (m/z): [M + ] calcd. C74H48N2O2 for, 996; found, 996 Example 14 : Synthesis of BD1-14
Figure 02_image149

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為2.2克N-苯基-3-二苯並呋喃基胺，可製備 BD1-14成品2.2克，純度99%，收率55%。經昇華純化後得1.6克產物。 Following the synthetic procedure in compound BD1-2 , changing 1.5 g of 4-methyldiphenylamine to 2.2 g of N-phenyl-3-dibenzofuranylamine, 2.2 g of BD1-14 product can be prepared with a purity of 99%. The yield is 55%. After purification by sublimation, 1.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.27(d, 1H), δ7.98(d, 1H) , δ7.87(s, 1H) , δ7.85-7.74(m, 5H) , δ7.67(d, 1H), δ7.62(d, 1H), δ7.56(s, 1H), δ7.49-7.05(m, 23H) , δ7.03-6.90(m, 8H) , δ1.56(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.27(d, 1H), δ7.98(d, 1H), δ7.87(s, 1H), δ7.85-7.74(m, 5H), δ7. 67(d, 1H), δ7.62(d, 1H), δ7.56(s, 1H), δ7.49-7.05(m, 23H), δ7.03-6.90(m, 8H), δ1.56 (s, 6H).

MS (m/z)：[M +] calcd. C 74H 48N 2O 2for, 996；found, 996 實施例 15 ： BD1-15 之合成

Figure 02_image151
MS (m/z): [M + ] calcd. C 74 H 48 N 2 O 2 for, 996; found, 996 Example 15 : Synthesis of BD1-15
Figure 02_image151

依循化合物 BD1-2中之合成程序，將1.5克4-甲基二苯胺改換為2.2克N-苯基-2-二苯並呋喃基胺，可製備 BD1-15成品1.8克，純度99%，收率45%。經昇華純化後得1.4克產物。 Following the synthesis procedure in compound BD1-2 , 1.5 g of 4-methyldiphenylamine was changed to 2.2 g of N-phenyl-2-dibenzofuranylamine, 1.8 g of BD1-15 product can be prepared, with a purity of 99%. The yield is 45%. 1.4 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.26(d, 1H), δ7.95(d, 1H) , δ7.86(s, 1H) , δ7.84-7.70(m, 5H) , δ7.66(d, 1H), δ7.60(d, 1H), δ7.54(s, 1H), δ7.50-7.08(m, 21H) , δ7.03-6.92(m, 10H) , δ1.56(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.26(d, 1H), δ7.95(d, 1H), δ7.86(s, 1H), δ7.84-7.70(m, 5H), δ7. 66(d, 1H), δ7.60(d, 1H), δ7.54(s, 1H), δ7.50-7.08(m, 21H), δ7.03-6.92(m, 10H), δ1.56 (s, 6H).

MS (m/z)：[M +] calcd. C 74H 48N 2O 2for, 996；found, 996 實施例 16 ： BD2-3 之合成

Figure 02_image153
MS (m/z): [M + ] calcd. C 74 H 48 N 2 O 2 for, 996; found, 996 Example 16 : Synthesis of BD2-3
Figure 02_image153

在氮氣下於三頸瓶中置入3.1克中間體C2(Intermediate C2)與1.7克3,3'-二甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.3克第三丁醇鉀，0.09克乙酸鈀，0.21克三第三丁基膦，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2.4克，純度99%，產率60%。經昇華純化後得1.6克產物。Put 3.1 g of Intermediate C2 (Intermediate C2) and 1.7 g of 3,3'-dimethyldiphenylamine, 40 ml of toluene (Tol) into a three-necked flask under nitrogen, stir to dissolve and add 1.3 g of potassium tert-butoxide, 0.09 g of palladium acetate, 0.21 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 2.4 g of product, purity 99%, yield 60%. After purification by sublimation, 1.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.30(d, 1H), δ7.94(d, 1H), δ7.84-7.74(m, 4H), δ7.53(s, 1H), δ7.38-7.15(m, 12H) , δ7.07-6.69(m, 24H) , δ6.55(d, 1H), δ2.15(s, 6H), δ2.13(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.30(d, 1H), δ7.94(d, 1H), δ7.84-7.74(m, 4H), δ7.53(s, 1H), δ7. 38-7.15(m, 12H), δ7.07-6.69(m, 24H), δ6.55(d, 1H), δ2.15(s, 6H), δ2.13(s, 6H).

MS (m/z)：[M +] calcd. C 76H 56N 2for, 996；found, 996 實施例 17 ： BD2-4 之合成

Figure 02_image155
MS (m/z): [M + ] calcd. C 76 H 56 N 2 for, 996; found, 996 Example 17 : Synthesis of BD2-4
Figure 02_image155

依循化合物 BD2-3中之合成程序，將1.7克3,3'-二甲基二苯胺改換為1.8克N-苯基-2-萘胺，可製備 BD2-4成品2.0克，純度99%，收率48%。經昇華純化後得1.5克產物。 Following the synthetic procedure in compound BD2-3 , 1.7 g of 3,3'-dimethyldiphenylamine was changed to 1.8 g of N-phenyl-2-naphthylamine, 2.0 g of BD2-4 product can be prepared with a purity of 99%. The yield is 48%. After purification by sublimation, 1.5 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.30(d, 1H), δ7.95(d, 1H) , δ7.82(d, 4H) , δ7.66-7.01(m, 32H), δ6.95-6.78(m, 12H), δ6.74(s, 1H) , δ6.54(s, 1H). 1 H NMR (400MHz, CDCl 3 ): δ8.30(d, 1H), δ7.95(d, 1H), δ7.82(d, 4H), δ7.66-7.01(m, 32H), δ6. 95-6.78(m, 12H), δ6.74(s, 1H), δ6.54(s, 1H).

MS (m/z)：[M +] calcd. C 80H 52N 2for, 1040；found, 1040 實施例 18 ： BD2-7 之合成

Figure 02_image157
MS (m/z): [M + ] calcd. C 80 H 52 N 2 for, 1040; found, 1040 Example 18 : Synthesis of BD2-7
Figure 02_image157

依循化合物 BD2-3中之合成程序，將1.7克3,3'-二甲基二苯胺改換為2.2克N-苯基-4-二苯並呋喃基胺，可製備 BD2-7成品2.0克，純度99%，收率44%。經昇華純化後得1.1克產物。 Following the synthetic procedure in compound BD2-3 , 1.7 g of 3,3'-dimethyldiphenylamine was changed to 2.2 g of N-phenyl-4-dibenzofuranylamine to prepare 2.0 g of BD2-7 product, The purity is 99%, and the yield is 44%. After purification by sublimation, 1.1 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.27(d, 1H), δ8.04(d, 1H) , δ7.78-7.70(m, 6H) , δ7.59(s, 1H), δ7.54(d, 1H), δ7.51(d, 1H), δ7.43-6.95(m, 27H) , δ6.94-6.73(m, 11H) , δ6.65(d, 2H) , δ6.41(s, 1H). 1 H NMR (400MHz, CDCl 3 ): δ8.27(d, 1H), δ8.04(d, 1H), δ7.78-7.70(m, 6H), δ7.59(s, 1H), δ7. 54(d, 1H), δ7.51(d, 1H), δ7.43-6.95(m, 27H), δ6.94-6.73(m, 11H), δ6.65(d, 2H), δ6.41 (s, 1H).

MS (m/z)：[M +] calcd. C 84H 52N 2O 2for, 1120；found, 1120 實施例 19 ： BD3-3 之合成

Figure 02_image159
MS (m/z): [M + ] calcd. C 84 H 52 N 2 O 2 for, 1120; found, 1120 Example 19 : Synthesis of BD3-3
Figure 02_image159

在氮氣下於三頸瓶中置入3.0克中間體C3(Intermediate C3)與1.7克4,4'-二甲基二苯胺，40毫升甲苯(Tol)攪拌溶解加入1.3克第三丁醇鉀，0.09克乙酸鈀，0.21克三第三丁基膦，加熱迴流反應2小時，冷卻濃縮後析出固體，固體以甲苯 (Tol)再結晶2次，過濾得產物2.0克，純度99%，產率52%。經昇華純化後得0.8克產物。Put 3.0 g of Intermediate C3 (Intermediate C3) and 1.7 g of 4,4'-dimethyldiphenylamine, 40 ml of toluene (Tol) into a three-necked flask under nitrogen, and add 1.3 g of potassium tert-butoxide. 0.09 g of palladium acetate, 0.21 g of tri-tertiary butyl phosphine, heated under reflux for 2 hours, cooled and concentrated, a solid precipitated out, the solid was recrystallized twice with toluene (Tol), filtered to obtain 2.0 g of product, purity 99%, yield 52 %. 0.8 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.33(d, 1H), δ7.91(d, 1H) , δ7.88-7.80(m, 4H) , δ7.58(s, 1H), δ7.43-7.08(m, 12H), δ7.02(s, 1H), δ6.91-6.65(m, 21H) , δ6.44(d, 1H) , δ2.19(s, 6H) , δ2.15(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.33(d, 1H), δ7.91(d, 1H), δ7.88-7.80(m, 4H), δ7.58(s, 1H), δ7. 43-7.08(m, 12H), δ7.02(s, 1H), δ6.91-6.65(m, 21H), δ6.44(d, 1H), δ2.19(s, 6H), δ2.15 (s, 6H).

MS (m/z)：[M +] calcd. C 76H 54N 2for, 994；found, 994 實施例 20 ： BD3-4 之合成

Figure 02_image161
MS (m/z): [M + ] calcd. C 76 H 54 N 2 for, 994; found, 994 Example 20 : Synthesis of BD3-4
Figure 02_image161

依循化合物 BD3-3中之合成程序，將1.7克4,4'-二甲基二苯胺改換為1.7克3,3'-二甲基二苯胺，可製備 BD3-4成品2.6克，純度99%，收率65%。經昇華純化後得1.9克產物。 Following the synthesis procedure in compound BD3-3 , 1.7 g of 4,4'-dimethyldiphenylamine was changed to 1.7 g of 3,3'-dimethyldiphenylamine, and 2.6g of BD3-4 product can be prepared with a purity of 99%. , The yield is 65%. After purification by sublimation, 1.9 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.35(d, 1H), δ7.93(d, 1H), δ7.84-7.74(m, 4H), δ7.55(s, 1H), δ7.41-7.11(m, 12H) , δ7.05-6.68(m, 22H) , δ6.56(d, 1H), δ2.16(s, 6H), δ2.13(s, 6H). 1 H NMR (400MHz, CDCl 3 ): δ8.35(d, 1H), δ7.93(d, 1H), δ7.84-7.74(m, 4H), δ7.55(s, 1H), δ7. 41-7.11(m, 12H), δ7.05-6.68(m, 22H), δ6.56(d, 1H), δ2.16(s, 6H), δ2.13(s, 6H).

MS (m/z)：[M +] calcd. C 76H 54N 2for, 994；found, 994 實施例 21 ： BD3-7 之合成

Figure 02_image163
MS (m/z): [M + ] calcd. C 76 H 54 N 2 for, 994; found, 994 Example 21 : Synthesis of BD3-7
Figure 02_image163

依循化合物 BD3-3中之合成程序，將1.7克4,4'-二甲基二苯胺改換為1.8克N-苯基-2-萘胺，可製備 BD3-7成品2.4克，純度99%，收率59%。經昇華純化後得1.6克產物。 Following the synthetic procedure in compound BD3-3 , changing 1.7 g of 4,4'-dimethyldiphenylamine to 1.8 g of N-phenyl-2-naphthylamine, 2.4 g of BD3-7 finished product with a purity of 99% can be prepared. The yield was 59%. After purification by sublimation, 1.6 g of product was obtained.

1H NMR (400MHz, CDCl 3)：δ8.36(d, 1H), δ7.93(d, 1H) , δ7.80(d, 4H) , δ7.66-7.01(m, 30H), δ6.95-6.78(m, 12H), δ6.72(s, 1H) , δ6.50(s, 1H). 1 H NMR (400MHz, CDCl 3 ): δ8.36(d, 1H), δ7.93(d, 1H), δ7.80(d, 4H), δ7.66-7.01(m, 30H), δ6. 95-6.78(m, 12H), δ6.72(s, 1H), δ6.50(s, 1H).

MS (m/z)：[M +] calcd. C 80H 50N 2for,1038；found, 1039 實施例 22 ： BD3-13 之合成

Figure 02_image165
MS (m/z): [M + ] calcd. C 80 H 50 N 2 for, 1038; found, 1039 Example 22 : Synthesis of BD3-13
Figure 02_image165

依循化合物 BD3-3中之合成程序，將1.7克4,4'-二甲基二苯胺改換為2.2克N-苯基-4-二苯並呋喃基胺，可製備 BD3-13成品2.0克，純度99%，收率45%。經昇華純化後得0.8克產物。 Following the synthetic procedure in compound BD3-3 , 1.7 g of 4,4'-dimethyldiphenylamine was changed to 2.2 g of N-phenyl-4-dibenzofuranylamine to prepare 2.0 g of BD3-13 product. The purity is 99%, and the yield is 45%. 0.8 g of product was obtained after purification by sublimation.

1H NMR (400MHz, CDCl 3)：δ8.34(d, 1H), δ8.02(d, 1H) , δ7.80-7.74(m, 6H) , δ7.60(s, 1H), δ7.57(d, 1H), δ7.53(d, 1H), δ7.43-7.21(m, 12H) , δ7.12-6.95(m, 13H) , δ6.94-6.73(m, 11H) , δ6.62(d, 2H) , δ6.38(s, 1H). 1 H NMR (400MHz, CDCl 3 ): δ8.34(d, 1H), δ8.02(d, 1H), δ7.80-7.74(m, 6H), δ7.60(s, 1H), δ7. 57(d, 1H), δ7.53(d, 1H), δ7.43-7.21(m, 12H), δ7.12-6.95(m, 13H), δ6.94-6.73(m, 11H), δ6 .62(d, 2H), δ6.38(s, 1H).

MS (m/z)：[M +] calcd. C 84H 50N 2O 2for, 1119；found, 1120 MS (m/z): [M + ] calcd. C 84 H 50 N 2 O 2 for, 1119; found, 1120

特別說明的是，雖然上述實施例9-22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[0026]段所述第4步之反應)便可合成出多種不同的產物，其組合可如下表1、表2所示：

Figure 02_image167
二級胺                中間體C1                                                                     產物(成品材料) In particular, although different materials and their synthesis methods are described in the foregoing Examples 9-22, the materials of the present invention are not limited thereto. According to the synthesis method of the above-mentioned examples, different starting materials are prepared, and then through the Buchwald-hartwig coupling reaction (ie, the reaction in step 4 described in paragraph [0026]), a variety of different products can be synthesized, and the combination can be as follows 1. As shown in Table 2:
Figure 02_image167
Secondary amine intermediate C1 product (finished material)

表1  Buchwald-hartwig偶聯反應起始物與產物對照表

Figure 02_image169
二級胺 中間體C1 (實施例3) 中間體C2 (實施例5) 中間體C3 (實施例8)
Figure 02_image171
 BD1-1   BD3-1
Figure 02_image173
 BD1-2 BD2-1 BD3-2
Figure 02_image175
 BD1-3 BD2-2 BD3-3
Figure 02_image177
 BD1-4 BD2-3 BD3-4
Figure 02_image179
 BD1-5   BD3-5
Figure 02_image181
 BD1-6   BD3-6
Figure 02_image183
 BD1-7 BD2-4 BD3-7
Figure 02_image185
 BD1-8 BD2-5 BD3-8
Figure 02_image187
 BD1-9   BD3-9
Figure 02_image189
 BD1-10   BD3-10
Figure 02_image191
 BD1-11 BD2-6 BD3-11
Figure 02_image193
 BD1-12   BD3-12
Figure 02_image195
 BD1-13 BD2-7 BD3-13
Figure 02_image197
 BD1-14 BD2-8 BD3-14
Figure 02_image199
 BD1-15   BD3-15
Figure 02_image201
 BD1-16 BD2-9 BD3-16
Figure 02_image203
 BD1-17    
Figure 02_image205
 BD1-18   BD3-17
Figure 02_image207
 BD1-19   BD3-18
Figure 02_image209
 BD1-20    
Figure 02_image211
 BD1-21     Table 1 Comparison table of starting materials and products of Buchwald-hartwig coupling reaction
Figure 02_image169
Secondary amine Intermediate C1 (Example 3) Intermediate C2 (Example 5) Intermediate C3 (Example 8)
Figure 02_image171
 BD1-1 BD3-1
Figure 02_image173
 BD1-2 BD2-1 BD3-2
Figure 02_image175
 BD1-3 BD2-2 BD3-3
Figure 02_image177
 BD1-4 BD2-3 BD3-4
Figure 02_image179
 BD1-5 BD3-5
Figure 02_image181
 BD1-6 BD3-6
Figure 02_image183
 BD1-7 BD2-4 BD3-7
Figure 02_image185
 BD1-8 BD2-5 BD3-8
Figure 02_image187
 BD1-9 BD3-9
Figure 02_image189
 BD1-10 BD3-10
Figure 02_image191
 BD1-11 BD2-6 BD3-11
Figure 02_image193
 BD1-12 BD3-12
Figure 02_image195
 BD1-13 BD2-7 BD3-13
Figure 02_image197
 BD1-14 BD2-8 BD3-14
Figure 02_image199
 BD1-15 BD3-15
Figure 02_image201
 BD1-16 BD2-9 BD3-16
Figure 02_image203
 BD1-17
Figure 02_image205
 BD1-18 BD3-17
Figure 02_image207
 BD1-19 BD3-18
Figure 02_image209
 BD1-20
Figure 02_image211
 BD1-21

表2  本發明BD化合物代號與結構式對照

Figure 02_image009
Figure 02_image011
Figure 02_image013
 BD1-1 BD1-2 BD1-3
Figure 02_image015
Figure 02_image017
Figure 02_image019
 BD1-4 BD1-5 BD1-6
Figure 02_image021
Figure 02_image023
Figure 02_image025
 BD1-7 BD1-8 BD1-9
Figure 02_image027
Figure 02_image029
Figure 02_image031
 BD1-10 BD1-11 BD1-12
Figure 02_image033
Figure 02_image035
Figure 02_image037
 BD1-13 BD1-14 BD1-15
Figure 02_image039
Figure 02_image041
Figure 02_image043
 BD1-16 BD1-17 BD1-18
Figure 02_image045
Figure 02_image047
Figure 02_image049
 BD1-19 BD1-20 BD1-21
Figure 02_image051
Figure 02_image053
Figure 02_image055
 BD2-1 BD2-2 BD2-3
Figure 02_image057
Figure 02_image059
Figure 02_image061
 BD2-4 BD2-5 BD2-6
Figure 02_image063
Figure 02_image065
Figure 02_image067
 BD2-7 BD2-8 BD2-9
Figure 02_image069
Figure 02_image071
Figure 02_image073
 BD3-1 BD3-2 BD3-3
Figure 02_image075
Figure 02_image077
Figure 02_image079
 BD3-4 BD3-5 BD3-6
Figure 02_image081
Figure 02_image083
Figure 02_image085
 BD3-7 BD3-8 BD3-9
Figure 02_image087
Figure 02_image089
Figure 02_image091
 BD3-10 BD3-11 BD3-12
Figure 02_image093
Figure 02_image095
Figure 02_image097
 BD3-13 BD3-14 BD3-15
Figure 02_image099
Figure 02_image101
 及
Figure 02_image103
。 BD3-16 BD3-17 BD3-18 Table 2 Comparison of code and structural formula of BD compound of the present invention
Figure 02_image009
Figure 02_image011
Figure 02_image013
 BD1-1 BD1-2 BD1-3
Figure 02_image015
Figure 02_image017
Figure 02_image019
 BD1-4 BD1-5 BD1-6
Figure 02_image021
Figure 02_image023
Figure 02_image025
 BD1-7 BD1-8 BD1-9
Figure 02_image027
Figure 02_image029
Figure 02_image031
 BD1-10 BD1-11 BD1-12
Figure 02_image033
Figure 02_image035
Figure 02_image037
 BD1-13 BD1-14 BD1-15
Figure 02_image039
Figure 02_image041
Figure 02_image043
 BD1-16 BD1-17 BD1-18
Figure 02_image045
Figure 02_image047
Figure 02_image049
 BD1-19 BD1-20 BD1-21
Figure 02_image051
Figure 02_image053
Figure 02_image055
 BD2-1 BD2-2 BD2-3
Figure 02_image057
Figure 02_image059
Figure 02_image061
 BD2-4 BD2-5 BD2-6
Figure 02_image063
Figure 02_image065
Figure 02_image067
 BD2-7 BD2-8 BD2-9
Figure 02_image069
Figure 02_image071
Figure 02_image073
 BD3-1 BD3-2 BD3-3
Figure 02_image075
Figure 02_image077
Figure 02_image079
 BD3-4 BD3-5 BD3-6
Figure 02_image081
Figure 02_image083
Figure 02_image085
 BD3-7 BD3-8 BD3-9
Figure 02_image087
Figure 02_image089
Figure 02_image091
 BD3-10 BD3-11 BD3-12
Figure 02_image093
Figure 02_image095
Figure 02_image097
 BD3-13 BD3-14 BD3-15
Figure 02_image099
Figure 02_image101
 and
Figure 02_image103
. BD3-16 BD3-17 BD3-18

表1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1、表2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BD。 實施例 23 ：玻璃轉移溫度 (Tg) 之測量 In Table 1, 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 Table 1 and Table 2 above, a variety of different luminescent materials BD can be synthesized by the Buchwald-hartwig coupling reaction of different secondary amines and intermediate C easily. Example 23 : 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3：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 3 below:

表3 實施例與比較例材料的Tg(玻璃轉移溫度) 材料 Tg (℃) BD1-2 181.9 BD1-3 189.5 BD1-4 171.4 BD1-7 193.3 BD1-13 190.0 BD1-14 206.8 BD1-15 189.1 BD2-3 182.6 BD2-4 207.2 BD2-7 194.2 BD3-3 206.0 BD3-4 198.2 BD3-7 217.4 BD3-13 207.11 BD-S1  (比較例1) ~115 BD-S2 (比較例2) ~150

Figure 02_image260
Figure 02_image262
BD-S1                                                     BD-S2 Table 3 Tg (Glass Transition Temperature) of Examples and Comparative Examples material Tg (℃) BD1-2 181.9 BD1-3 189.5 BD1-4 171.4 BD1-7 193.3 BD1-13 190.0 BD1-14 206.8 BD1-15 189.1 BD2-3 182.6 BD2-4 207.2 BD2-7 194.2 BD3-3 206.0 BD3-4 198.2 BD3-7 217.4 BD3-13 207.11 BD-S1 (Comparative Example 1) ~115 BD-S2 (Comparative Example 2) ~150
Figure 02_image260
Figure 02_image262
BD-S1 BD-S2

由表3可知，本發明之材料的玻璃轉移溫度Tg，除BD1-4為171.4℃外，其餘材料皆高於180℃，較目前常用之藍色發光層客體材料(比較例1與2) 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 24 ：元件測試 It can be seen from Table 3 that the glass transition temperature Tg of the material of the present invention, except for BD1-4 which is 171.4°C, the other materials are all higher than 180°C, which is higher than that of the commonly used blue light-emitting layer guest materials (Comparative Examples 1 and 2) Higher glass transition temperature and higher thermal stability are suitable for industrial processes. Embodiment 24 : 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。It is particularly noted that the organic electroluminescent device of the present invention is not limited to the above-mentioned aspect in practical application, 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BD，另外採用習知藍光客體發光材料BD-S1, BD-S2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4：The organic electroluminescent device of the present invention is characterized in that the guest material of the light-emitting layer is the compound BD of formula (I), and the conventional blue guest light-emitting materials BD-S1 and BD-S2 are used as comparative examples. 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 4 below:

表4 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：α,β-ADN 客體：本發明BD或比較例BD-S1, BD-S2 5% (30nm) 電子傳輸層(ETL)6 ET 25nm 陰極層7 LiF 1nm, Al 150nm

Figure 02_image264
Figure 02_image266
Figure 02_image268
Figure 02_image270
Figure 02_image272
Figure 02_image274
Table 4 The materials of each layer of the organic excitation light 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 Luminous layer 5 Host: α, β-ADN Object: BD of the present invention or comparative examples BD-S1, BD-S2 5% (30nm) Electron Transport Layer (ETL) 6 ET 25nm Cathode layer 7 LiF 1nm, Al 150nm
Figure 02_image264
Figure 02_image266
Figure 02_image268
Figure 02_image270
Figure 02_image272
Figure 02_image274

使用上述BD系列材料作為客體發光材料，發光層的發光波長介於450至490 nm之間，屬於藍光發光材料。The above BD series materials are used as guest light-emitting materials, and the light-emitting layer has a light-emitting wavelength between 450 and 490 nm, which is a blue light-emitting material.

使用本發明實施例之各種材料，以及傳統材料BD-S1, BD-S2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5所示：The test results of the organic electroluminescence device using the various materials of the embodiments of the present invention and the traditional materials BD-S1 and BD-S2 as the light-emitting guest materials are shown in Table 5 below:

表5 實施例與比較例之有機電激發光裝置的特性 實施例 Dopant Voltage* (V) EL max (nm) EQE* CE* (Cd/A) LT 50@150mA (hr) 1 BD1-2 6.18 465 8.50% 11.6 205 2 BD1-3 5.86 471 7.96% 12.2 234 3 BD1-4 6.28 464 7.93% 9.4 156 4 BD1-7 6.44 465 8.10% 10.6 173 5 BD1-13 6.80 458 8.69% 9.2 312 6 BD1-14 5.85 471 8.18% 10.2 363 7 BD3-4 6.05 466 8.78% 11.2 167 8 BD3-7 6.08 468 7.95% 10.2 251 9 BD3-13 6.59 460 9.24% 10.5 350 比較例1 BD-S1 7.15 462 7.28% 7.2 107 比較例2 BD-S2 6.82 465 7.52% 8.9 120 *在電流密度100 mA/cm 2下的測量值 Table 5 The characteristics of the organic electroluminescence device of the embodiment and the comparative example Example Dopant Voltage * (V) EL max (nm) EQE* CE* (Cd/A) LT 50 @150mA (hr) 1 BD1-2 6.18 465 8.50% 11.6 205 2 BD1-3 5.86 471 7.96% 12.2 234 3 BD1-4 6.28 464 7.93% 9.4 156 4 BD1-7 6.44 465 8.10% 10.6 173 5 BD1-13 6.80 458 8.69% 9.2 312 6 BD1-14 5.85 471 8.18% 10.2 363 7 BD3-4 6.05 466 8.78% 11.2 167 8 BD3-7 6.08 468 7.95% 10.2 251 9 BD3-13 6.59 460 9.24% 10.5 350 Comparative example 1 BD-S1 7.15 462 7.28% 7.2 107 Comparative example 2 BD-S2 6.82 465 7.52% 8.9 120 *Measured value under current density of 100 mA/cm 2

由表5可知，使用本發明之藍光發光材料的有機電激發光裝置，與使用傳統藍光發光材料BD-S1與BD-S2的有機電激發光裝置相比較(比較例1與2)，其在電流密度100 mA/cm 2時導通電壓(Turn-on voltage)較低，最高降低可達17%(7.15→5.85 V)，為低阻抗材料。因本發明化合物(I)具有(雙)螺環結構，能有效減少分子堆疊，降低分子-分子本身激子粹息現象發生(exciton quenching)，提高元件效率，故可具有較高的外部量子效率(External Quantum Efficiency, EQE)，最高提升達27%(7.28→9.24%)，以及較高的電流效率(Current Efficiency, CE)，最高提升達30%(8.9→11.6 Cd/A，在EL=465 nm時)。而以使用發光材料BD1-13與BD3-13的裝置來說，更可以發出更深藍的光(較低ELmax)。故此系列材料具高效率與深藍光色特性，具有產業應用價值。 It can be seen from Table 5 that the organic electroluminescent device using the blue light-emitting material of the present invention is compared with the organic electroluminescent device using traditional blue light-emitting materials BD-S1 and BD-S2 (Comparative Examples 1 and 2). When the current density is 100 mA/cm 2 , the turn-on voltage is low, and the maximum reduction can reach 17% (7.15→5.85 V). It is a low-impedance material. Because the compound (I) of the present invention has a (double) spiro ring structure, it can effectively reduce molecular stacking, reduce the exciton quenching of the molecule-molecule itself, and improve the efficiency of the element, so it can have a higher external quantum efficiency (External Quantum Efficiency, EQE), up to 27% (7.28→9.24%), and higher current efficiency (Current Efficiency, CE), up to 30% (8.9→11.6 Cd/A, at EL=465 nm). In the case of devices using the luminescent materials BD1-13 and BD3-13, it can emit darker blue light (lower ELmax). Therefore, this series of materials has high efficiency and deep blue color characteristics, and has industrial application value.

另，如實施例23之表3可知，本發明化合物具有更高的玻璃轉移溫度，可使元件獲得更長的壽命。在一實施例中，元件壽命由107小時提高到了363小時，提升達239%。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。In addition, as shown in Table 3 of Example 23, the compound of the present invention has a higher glass transition temperature, which enables the device to obtain a longer life. In one embodiment, the component life is increased from 107 hours to 363 hours, an increase of 239%. In addition, the above-mentioned materials have simple preparation methods, are 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 embodiments, these embodiments 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 appended 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、經取代的苯基或未取代的苯基，其中當兩個R皆為苯基時，兩苯基間可以單鍵連結。 A material for an organic electroluminescence device, which has the structure shown in the following chemical formula (I):
Figure 03_image001
(I); where 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 For heteroaryl groups containing oxygen atoms, each R is independently a C 1 to C 4 alkyl group, a substituted phenyl group or an unsubstituted phenyl group, wherein when both R are phenyl groups, there may be a single bond between the two phenyl groups link. 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
 BD1-1 BD1-2 BD1-3
Figure 03_image015
Figure 03_image017
Figure 03_image019
 BD1-4 BD1-5 BD1-6
Figure 03_image021
Figure 03_image023
Figure 03_image025
 BD1-7 BD1-8 BD1-9
Figure 03_image027
Figure 03_image029
Figure 03_image031
 BD1-10 BD1-11 BD1-12
Figure 03_image033
Figure 03_image035
Figure 03_image037
 BD1-13 BD1-14 BD1-15
Figure 03_image039
Figure 03_image041
Figure 03_image043
 BD1-16 BD1-17 BD1-18
Figure 03_image045
Figure 03_image047
Figure 03_image049
 BD1-19 BD1-20 BD1-21
Figure 03_image051
Figure 03_image053
Figure 03_image055
 BD2-1     BD2-2     BD2-3    
Figure 03_image057
Figure 03_image059
Figure 03_image061
 BD2-4 BD2-5 BD2-6
Figure 03_image063
Figure 03_image065
Figure 03_image067
 BD2-7 BD2-8 BD2-9
Figure 03_image069
Figure 03_image071
Figure 03_image073
 BD3-1 BD3-2 BD3-3
Figure 03_image075
Figure 03_image077
Figure 03_image079
 BD3-4 BD3-5 BD3-6
Figure 03_image081
Figure 03_image083
Figure 03_image085
 BD3-7 BD3-8 BD3-9
Figure 03_image087
Figure 03_image089
Figure 03_image091
 BD3-10 BD3-11 BD3-12
Figure 03_image093
Figure 03_image095
Figure 03_image097
 BD3-13 BD3-14 BD3-15
Figure 03_image099
Figure 03_image101
 及
Figure 03_image103
。 BD3-16 BD3-17 BD3-18
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
 BD1-1 BD1-2 BD1-3
Figure 03_image015
Figure 03_image017
Figure 03_image019
 BD1-4 BD1-5 BD1-6
Figure 03_image021
Figure 03_image023
Figure 03_image025
 BD1-7 BD1-8 BD1-9
Figure 03_image027
Figure 03_image029
Figure 03_image031
 BD1-10 BD1-11 BD1-12
Figure 03_image033
Figure 03_image035
Figure 03_image037
 BD1-13 BD1-14 BD1-15
Figure 03_image039
Figure 03_image041
Figure 03_image043
 BD1-16 BD1-17 BD1-18
Figure 03_image045
Figure 03_image047
Figure 03_image049
 BD1-19 BD1-20 BD1-21
Figure 03_image051
Figure 03_image053
Figure 03_image055
 BD2-1 BD2-2 BD2-3
Figure 03_image057
Figure 03_image059
Figure 03_image061
 BD2-4 BD2-5 BD2-6
Figure 03_image063
Figure 03_image065
Figure 03_image067
 BD2-7 BD2-8 BD2-9
Figure 03_image069
Figure 03_image071
Figure 03_image073
 BD3-1 BD3-2 BD3-3
Figure 03_image075
Figure 03_image077
Figure 03_image079
 BD3-4 BD3-5 BD3-6
Figure 03_image081
Figure 03_image083
Figure 03_image085
 BD3-7 BD3-8 BD3-9
Figure 03_image087
Figure 03_image089
Figure 03_image091
 BD3-10 BD3-11 BD3-12
Figure 03_image093
Figure 03_image095
Figure 03_image097
 BD3-13 BD3-14 BD3-15
Figure 03_image099
Figure 03_image101
 and
Figure 03_image103
. BD3-16 BD3-17 BD3-18
如申請專利範圍第1至3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 3 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 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 material described in any one of items 1 to 4 in the scope of patent application. 如申請專利範圍第5項所述之裝置，其中該發光層的發光波長介於450-490 nm。The device described in item 5 of the scope of patent application, wherein the emission wavelength of the light-emitting layer is between 450-490 nm. 如申請專利範圍第5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。The device according to claim 5, wherein a hole injection layer is further included between the anode layer and the hole transport layer. 如申請專利範圍第5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。The device described in item 5 of the scope of patent application, wherein an electron injection layer is further included between the electron transport layer and the cathode layer. 如申請專利範圍第5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。The device according to claim 5, wherein 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5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。In the device described in item 5 of the scope of patent application, 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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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200808683A (en) * 2006-07-11 2008-02-16 Merck Patent Gmbh Novel materials for organic electroluminescent devices
TW201432021A (en) * 2012-09-04 2014-08-16 Merck Patent Gmbh Compounds for electronic devices
CN111153810A (en) * 2020-01-15 2020-05-15 合肥鼎材科技有限公司 Compound, application thereof and organic electroluminescent device containing compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200808683A (en) * 2006-07-11 2008-02-16 Merck Patent Gmbh Novel materials for organic electroluminescent devices
TW201432021A (en) * 2012-09-04 2014-08-16 Merck Patent Gmbh Compounds for electronic devices
CN111153810A (en) * 2020-01-15 2020-05-15 合肥鼎材科技有限公司 Compound, application thereof and organic electroluminescent device containing compound

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