CN108164462A - One kind is used as nitrogen-containing heterocycle compound and the application of luminescent material - Google Patents

One kind is used as nitrogen-containing heterocycle compound and the application of luminescent material Download PDF

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CN108164462A
CN108164462A CN201810125434.2A CN201810125434A CN108164462A CN 108164462 A CN108164462 A CN 108164462A CN 201810125434 A CN201810125434 A CN 201810125434A CN 108164462 A CN108164462 A CN 108164462A
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nitrogen
luminescent material
naphthalene
wavelength
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吴建德
丰佩川
胡灵峰
张国选
杨阳
王磊
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YANTAI XIANHUA CHEM-TECH Co Ltd
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YANTAI XIANHUA CHEM-TECH Co Ltd
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Abstract

The invention belongs to organic photoelectrical material technical field more particularly to a kind of nitrogen-containing heterocycle compound for being used as luminescent material and applications.Not only luminous efficiency is high, but also the wavelength for emitting light can be adjusted in the range of as main body luminescent material for nitrogen heterocyclic ring produced by the present invention, and maximum luminous wavelength can be 410 530nm.Such material has similar skeleton structure, and HOMO LUMO can be all high, can be Jiang Neng amount Chuan Di Give object luminiferous materials, so as to fulfill wavelength of transmitted light from blue light to the adjusting of green optical range, it is particularly suitable to improve luminous efficiency in display devices, reduce driving voltage.In addition, the preparation method of main body luminescent material is essentially identical, it is easy to operate.

Description

One kind is used as nitrogen-containing heterocycle compound and the application of luminescent material
Technical field
The invention belongs to organic photoelectrical material technical field more particularly to a kind of nitrogen heterocyclic ring chemical combination for being used as luminescent material Object and application.
Background technology
Organic Light Emitting Diode (English name Organic Light Emitting Diode, abbreviation OLED) is one kind by having The solid-state devices of machine material film composition, can shine after applying voltage.Compared to traditional light emitting diode (LED) and liquid crystal It shows (LCD), OLED has wide self-luminous, clear beautiful, frivolous, fast response time, visual angle, low-power consumption, Applicable temperature range Greatly, the features such as manufacturing process is simple.OLED can do the dreamlike display for being rolled over everywhere as imaging wallpaper, rolling up, paste, hanging, and be expected to take For liquid crystal display, it is known as " ultimate display technology ".In addition, OLED is as planar light source, either in structure or in light Source quality, selling point etc. all have the advantage that traditional LED illumination can not reach.
Invention content
The present invention in view of the deficiency of the prior art, provides a kind of nitrogen-containing heterocycle compound for being used as luminescent material And application.
The technical solution that the present invention solves above-mentioned technical problem is as follows：One kind is used as the nitrogen heterocyclic ring chemical combination of luminescent material Object, structural formula are as follows：
Wherein, R1、R3、R4、R6、R7、R8、R9It is each independently hydrogen, alkyl, silylation, halogen, CN, SCN, NO2、CF3 Or aromatic group；X is C, N or B；
R5、R10It is each independently hydrogen, deuterium, alkyl, cycloalkyl, hydroxyl, amino, sulfydryl, alkenyl, alkynyl, aryl, heteroaryl Base, alkoxy, aryloxy group, amido, silylation, halogen, CN, SCN, NO2、CF3,=,
Preferably, above-mentioned nitrogen-containing heterocycle compound, structural formula are respectively：
Second object of the present invention is to provide above-mentioned nitrogen-containing heterocycle compound as electroluminescent material, in Organic Electricity Application in electroluminescence device.
The beneficial effects of the invention are as follows：Nitrogen heterocyclic ring produced by the present invention is as main body luminescent material not only luminous efficiency Height, and the wavelength for emitting light can be adjusted in the range of, and maximum luminous wavelength can be 410-530nm.Such material has phase Near skeleton structure, HOMO-LUMO can be all high, can be Jiang Neng amount Chuan Di Give object luminiferous materials, so as to fulfill wavelength of transmitted light It is particularly suitable to improve luminous efficiency in display devices from blue light to the adjusting of green optical range, reduce driving electricity Pressure.In addition, the preparation method of main body luminescent material is essentially identical, it is easy to operate.
Description of the drawings
Fig. 1 is the structure diagram of organic electroluminescence device；
Fig. 2 is the emission spectroanalysis figure of application examples 1；
Fig. 3 is the emission spectroanalysis figure of application examples 2；
Fig. 4 is the emission spectroanalysis figure of application examples 3；
Fig. 5 is the emission spectroanalysis figure of application examples 4；
Fig. 6 is the emission spectroanalysis figure of application examples 5；
Fig. 7 is the emission spectroanalysis figure of application examples 6；
In figure, 1, glass substrate；2nd, anode layer；3rd, hole injection layer；4th, hole transmission layer；5th, luminescent layer；6th, electronics passes Defeated layer；7th, electron injecting layer；8th, cathode layer.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
Each raw material mix formula used in the embodiment of the present invention is as follows：
Embodiment 1
The synthesis of compound (1), reaction equation are as follows：(1) synthetic intermediate A1
(2) synthetic intermediate A2
(3) synthetic intermediate A3
(4) prepare compound (1)
Specific preparation method is as follows：
(1) by 3,9- dimethylbiphenyls [G] quinoline (MW:207.2) 20.72g (0.1mol), N-bromosuccinimide (MW:177.98) 18.7g (0.105mol), DMF (N,N-dimethylformamide) (MW:73.09) 360mL, diphenyl peroxide first Acyl (MW:242.23) 0.84g (0.0035mol) is placed in 500mL reaction bulbs, is inserted into condenser pipe and thermometer, is stirred to react, and is risen Temperature reacts 12h, cools down after reaction to 100 DEG C, adds in 140ml ethyl alcohol, refilters, washes, dries, obtain 10- bromo- 3, 9 ,-dimethylbiphenyl [G] quinoline (A1) (MW:285.02) 26.22g, yield 92%；
(2) 1- naphthalene boronic acids (MW is taken:172) 17.2g (0.1mol), step (1) 10- bromo- 3,9 ,-dimethylbiphenyl [G] Quinoline (A1) (MW:285.02)26.22g(0.092mol)、Pd(PPh3)4(tetrakis triphenylphosphine palladium) (MW:1155.58) 1.06g, sodium carbonate (MW:106) 11.67g, toluene 250mL, ethyl alcohol 60mL and water 60mL are placed in 500mL reaction bulbs, are inserted into cold Solidifying pipe, thermometer, are stirred to react, and rise Warm to 65 DEG C, react 18h, cool down after reaction, add in 130mL ethyl alcohol, refilter, Washing, drying, obtain 3,9,-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:333.43) 27.6g, yield 90%；
(3) by the 3,9 of step (2),-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:333.43)27.34g (0.082mol), N-bromosuccinimide (MW:177.98) 15.43g (0.086mol), DMF (N,N-dimethylformamide) (MW:73.09) 300mL, dibenzoyl peroxide (MW:242.23) 0.7g (0.0029mol) is placed in 500mL reaction bulbs, is inserted Enter condenser pipe, thermometer, be stirred to react, be warming up to 100 DEG C, react 12h, cool down after reaction, add in 150mL ethyl alcohol, then Filtering, washing, drying, obtain 5- bromo- 3,9,-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:412.33)32.16g (0.078mol), yield 95%；
(4) by the 5- bromo- 3,9 of step (3),-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:412.33) 32.16g (0.078mol), (4- (1- naphthalenes) phenyl) boric acid (MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(four (triphens Base phosphine) palladium) (MW:1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, water 50mL are placed in In 500mL reaction bulbs, condenser pipe, thermometer are inserted into, is stirred to react, be warming up to 65 DEG C, reacted 18h, treat to cool down after reaction, 150mL ethyl alcohol is added in, refilters, wash, dry, obtain 3,9,-dimethyl -10- (naphthalene -1- bases) 5- (4 (naphthalene -1- bases) benzene) benzene And [G] quinoline (MW:535.69) 36.76g (0.06864mol), as compound (1), yield 88%.
Embodiment 2
The synthesis of compound (8), reaction equation are as follows：
Specific preparation method is as follows：
Step (1) (2) (3) is identical with the preparation method of embodiment 1, and difference lies in step (4)：
By the 5- bromo- 3,9 of step (3),-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:412.33)32.16g (0.078mol), 4- (naphthalene -2- bases) phenyl) boric acid (MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(four (triphenyls Phosphine) palladium) (MW:1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, water 50mL are placed in 500mL In reaction bulb, condenser pipe, thermometer are inserted into, is stirred to react, be warming up to 65 DEG C, reacted 18h, treat to cool down after reaction, added in 150mL ethyl alcohol refilters, washes, dries, obtains 3,9,-dimethyl -10- (naphthalene -1- bases) 5- (4 (naphthalene -2- bases) benzene) benzo [G] quinoline (MW:535.69) 36.76g (0.06864mol), as compound (8), yield 88%.
Embodiment 3
The synthesis of compound (57), reaction equation are as follows：
Specific preparation method is as follows：
Step (1) (2) (3) is identical with the preparation method of embodiment 1, and difference lies in step (4)：
By the 5- bromo- 3,9 of step (3),-dimethyl -10- (naphthalene -1- bases) benzo [G] quinoline (MW:412.33)32.16g (0.078mol), naphtho- (2,3-b) benzofuran -2- ylboronic acids (MW:262.08)22.53g(0.086mol)、Pd(PPh3)4 (tetrakis triphenylphosphine palladium) (MW:1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, water 50mL is placed in 500mL reaction bulbs, is inserted into condenser pipe, thermometer, is stirred to react, and is warming up to 65 DEG C, reacts 18h, treats reaction knot Cool down after beam, add in 150mL ethyl alcohol, refilter, wash, dry, obtain 3,9- dimethyl -10- (- 1 base of naphthalene) -5- (naphtho- (2, 3-b) benzofuran -2- bases) benzo [G] quinoline (MW:549.21) 36.84g (0.067mol), as compound (57), yield 86%.
Embodiment 4
The synthesis of compound (1a), reaction equation are as follows：(1) synthetic intermediate A1a
(2) synthetic intermediate A2a
(3) synthetic intermediate A3a
(4) prepare compound (1a)
Specific preparation method is as follows：
(1) by benzo [G] quinoline (MW:179) 17.9g (0.1mol), N-bromosuccinimide (MW:177.98) 18.7g (0.105mol), DMF (N,N-dimethylformamide) (MW:73.09) 360mL, dibenzoyl peroxide (MW: 242.23) 0.84g (0.0035mol) is placed in 500mL reaction bulbs, is inserted into condenser pipe and thermometer is stirred to react, be warming up to 100 DEG C, 12hrs is reacted, is cooled down after anti-Ying Knot beams, 140mL ethyl alcohol is added in, refilters, washes, dries, obtain 10- bromobenzenes simultaneously [G] Quinoline (A1a) (MW:256.98) 23.64g, yield 92%；
(2) 1- naphthalene boronic acids (MW is taken:172) 17.2g (0.1mol), step (1) 10- bromobenzenes simultaneously [G] quinoline (A1a) (MW: 256.98)23.6g(0.092mol)、Pd(PPh3)4(tetrakis triphenylphosphine palladium) (MW:1155.58) 1.06g, sodium carbonate (MW: 106) 11.67g, toluene 250mL, ethyl alcohol 60mL and water 60mL are placed in 500mL reaction bulbs, are inserted into condenser pipe, thermometer, stirring Reaction rises Warm to 65 DEG C, reacts 18h, cools down after reaction, adds in 130mL ethyl alcohol, refilters, washes, dries, obtain 10- (naphthalene -1- bases) benzo [G] quinoline (MW:304.39) 25.14g, yield 90%；
(3) by the 10- of step (2) (naphthalene -1- bases) benzo [G] quinoline (MW:304.39) 25.14g (0.082mol), N- bromines For succinimide (MW:177.98) 15.43g (0.086mol), DMF (N,N-dimethylformamide) (MW:73.09)300mL、 Dibenzoyl peroxide (MW:242.23) 0.7g (0.0029mol) is placed in 500mL reaction bulbs, is inserted into condenser pipe, thermometer, It is stirred to react, is warming up to 100 DEG C, react 12h, cool down after reaction, add in 150mL ethyl alcohol, refilter, wash, dry, obtain To the bromo- 10- of 5- (naphthalene -1- bases) benzo [G] quinoline (MW:383.29) 29.89g (0.078mol), yield 95%；
(4) by the bromo- 10- of 5- of step (3) (naphthalene -1- bases) benzo [G] quinoline (MW:383.29)29.89g (0.078mol), (4- (1- naphthalenes) phenyl) boric acid (MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(four (triphenylphosphines) Palladium) (MW:1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, that water 50mL is placed in 500mL is anti- It answers in bottle, is inserted into condenser pipe, thermometer, is stirred to react, be warming up to 65 DEG C, react 18h, treat to cool down after reaction, add in 150mL ethyl alcohol is refiltered, washes, is dried, and obtains 10- (naphthalene -1- bases) 5- (4 (naphthalene -1- bases) benzene) benzo [G] quinoline (MW: 507.6) 34.84g (0.06864mol), as compound (1a), yield 88%.
Embodiment 5
The synthesis of compound (8a), reaction equation are as follows：
Specific preparation method is as follows：
Step (1) (2) (3) is identical with the preparation method of embodiment 1, and difference lies in step (4)：
By the bromo- 10- of 5- (naphthalene -1- bases) benzo [G] quinoline (MW of step (3):383.29)29.89g(0.078mol)、4- (naphthalene -2- bases) phenyl) boric acid (MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(tetrakis triphenylphosphine palladium) (MW: 1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, water 50mL are placed in 500mL reaction bulbs, Condenser pipe, thermometer are inserted into, is stirred to react, is warming up to 65 DEG C, 18h is reacted, treats to cool down after reaction, adds in 150mL ethyl alcohol, It refilters, wash, dry, obtain 10- (naphthalene -1- bases) 5- (4 (naphthalene -2- bases) benzene) benzo [G] quinoline (MW:507.2)34.81g (0.06864mol), yield 88%.
Embodiment 6
The synthesis of compound (57a), reaction equation are as follows：
Specific preparation method is as follows：
Step (1) (2) (3) is identical with the preparation method of embodiment 1, and difference lies in step (4)：
By the bromo- 10- of 5- (naphthalene -1- bases) benzo [G] quinoline (MW of step (3):383.29) 29.89g (0.078mol), naphthalene And (2,3-b) benzofuran -2- ylboronic acids (MW:262.08)22.53g(0.086mol)、Pd(PPh3)4(four (triphenylphosphines) Palladium) (MW:1155.58) 0.9g, sodium carbonate (MW:106) 9.92g, toluene 250mL, ethyl alcohol 50mL, that water 50mL is placed in 500mL is anti- It answers in bottle, is inserted into condenser pipe, thermometer, is stirred to react, be warming up to 65 DEG C, react 18h, treat to cool down after reaction, add in 150mL ethyl alcohol is refiltered, washes, is dried, and obtains 10- (- 1 base of naphthalene) -5- (naphtho- (2,3-b) benzofuran -2- bases) benzo [G] quinoline (MW:549.21) 36.84g (0.067mol), as compound (57a), yield 86%.
As shown in Figure 1 and Figure 2, the structure of organic electroluminescence device (OLED) includes the glass substrate for stacking gradually combination 1st, anode layer 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and cathode layer 8.It will Luminescent material produced by the present invention is applied in the luminescent layer of OLED, each composition of layer compositions of the OLED that table 1 is application examples 1-3, table 2 Each composition of layer compositions of OLED for application examples 4-6.
Table 1
Table 2
Reference examples
Tin indium oxide (ITO) of a layer thickness for 100nm is deposited on glass bottom liner 1 as transparent anode layer 2；Transparent On anode layer 2 vacuum evaporation thickness be 10nm NPB (N, N '-two (1- naphthalenes)-N, N '-diphenyl -1,1 '-biphenyl -4-4 ' - Diamines) hole mobile material as hole injection layer 3, wherein doping mass ratio 3% F4-TCNQ (2,3,5,6- tetra- fluoro- 7, Tetra- cyanogen dimethyl-parabenzoquinone of 7', 8,8'-)；Be on hole injection layer 3 a layer thickness be 100nm spiro-TAD (2,2', 7, (the diphenyl amino) -9,9'- of 7'- tetra- spiro-bisfluorenes) as hole transmission layer 4；Vacuum evaporation a layer thickness on hole transmission layer 4 It is 20nm blue-fluorescence main bodys CBP (4,4'- bis- (9H- carbazole -9- bases) biphenyl) as luminescent layer 5, wherein doped with 3wt% indigo plants Color fluorescent dopants TMTP (tetra- toluene pyrenes of 1,3,6,8-)；Vacuum evaporation a layer thickness is 30nm successively on luminescent layer 5 again TPQ (2,3,5,8- tetraphenyl quinoxaline) as electron transfer layer 6, LiF that thickness is 1nm as electron injecting layer 7, finally Vacuum evaporation coating techniques of deposition thickness is used on electron injecting layer 7 as the moon of the metallic aluminium (Al) of 100nm as device Pole layer 8.
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 5%.
Application examples 1
Tin indium oxide (ITO) of a layer thickness for 100nm is deposited on glass bottom liner 1 as transparent anode layer 2；Transparent On anode layer 2 vacuum evaporation thickness be 10nm NPB (N, N '-two (1- naphthalenes)-N, N '-diphenyl -1,1 '-biphenyl -4-4 ' - Diamines) hole mobile material as hole injection layer 3, wherein doping mass ratio 3% F4-TCNQ (2,3,5,6- tetra- fluoro- 7, Tetra- cyanogen dimethyl-parabenzoquinone of 7', 8,8'-)；Be on hole injection layer 3 a layer thickness be 100nm spiro-TAD (2,2', 7, (the diphenyl amino) -9,9'- of 7'- tetra- spiro-bisfluorenes) as hole transmission layer 4；Vacuum evaporation a layer thickness on hole transmission layer 4 Be 20nm blue-fluorescences main body-compound (1) as luminescent layer 5, wherein doped with 3wt% blue-fluorescence dopants TMTP (1, Tetra- toluene pyrenes of 3,6,8-)；Vacuum evaporation a layer thickness is TPQ (the 2,3,5,8- tetraphenyls of 30nm successively on luminescent layer 5 again Quinoxaline) as electron transfer layer 6, thickness be 1nm LiF as electron injecting layer 7, finally used on electron injecting layer 7 Vacuum evaporation coating techniques of deposition thickness is cathode layer 8 of the metallic aluminium (Al) of 100nm as device.
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 7%.
Application examples 2
It is identical with application examples 1, with application examples 1 the difference lies in：Luminescent layer 5 is thickness 20nm blue-fluorescences main body-change Object (8) is closed as luminescent layer 5, wherein doped with 3wt% blue-fluorescences dopant (1,3,6,8- tetra- toluene pyrene).
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, color Blue Color, maximum external quantum efficiency are 8%.
Application examples 3
It is identical with application examples 1, with application examples 1 the difference lies in：Luminescent layer 5 is thickness 20nm blue-fluorescences main body-change Object (57) is closed as luminescent layer 5, wherein doped with 3wt% blue-fluorescences dopant (1,3,6,8- tetra- toluene pyrene).
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 7%.
Application examples 4
It is identical with application examples 1, with application examples 1 the difference lies in：Luminescent layer 5 is thickness 20nm blue-fluorescences main body-change Object (1a) is closed as luminescent layer 5, wherein doped with 3wt% blue-fluorescences dopant (1,3,6,8- tetra- toluene pyrene).
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 7%.
Application examples 5
It is identical with application examples 1, with application examples 1 the difference lies in：Luminescent layer 5 is thickness 20nm blue-fluorescences main body-change Object (8a) is closed as luminescent layer 5, wherein doped with 3wt% blue-fluorescences dopant (1,3,6,8- tetra- toluene pyrene).
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 8%.
Application examples 6
It is identical with application examples 1, with application examples 1 the difference lies in：Luminescent layer 5 is thickness 20nm blue-fluorescences main body-change Object (57a) is closed as luminescent layer 5, wherein doped with 3wt% blue-fluorescences dopant (1,3,6,8- tetra- toluene pyrene).
Know through performance test, the maximum luminous wavelength of the electroluminescent spectrum of the device is located at 490nm, and color is indigo plant Color, maximum external quantum efficiency are 7%.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (3)

1. one kind is used as the nitrogen-containing heterocycle compound of luminescent material, which is characterized in that its structural formula is as follows：
Wherein, R1、R3、R4、R6、R7、R8、R9It is each independently hydrogen, alkyl, silylation, halogen, CN, SCN, NO2、CF3Or virtue Perfume base group；X is C, N or B；
R5、R10Be each independently hydrogen, deuterium, alkyl, cycloalkyl, hydroxyl, amino, sulfydryl, alkenyl, alkynyl, aryl, heteroaryl, Alkoxy, aryloxy group, amido, silylation, halogen, CN, SCN, NO2、CF3,=,
2. nitrogen-containing heterocycle compound according to claim 1, which is characterized in that its structural formula is：
3. a kind of any one of claim 1-2 nitrogen-containing heterocycle compounds are as electroluminescent material, in organic electroluminescent Application in device.
CN201810125434.2A 2018-02-08 2018-02-08 One kind is used as nitrogen-containing heterocycle compound and the application of luminescent material Pending CN108164462A (en)

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