CN102633709B - Main luminophor material and organic light emitting diode containing same - Google Patents

Main luminophor material and organic light emitting diode containing same Download PDF

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CN102633709B
CN102633709B CN201210049723.1A CN201210049723A CN102633709B CN 102633709 B CN102633709 B CN 102633709B CN 201210049723 A CN201210049723 A CN 201210049723A CN 102633709 B CN102633709 B CN 102633709B
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carbazole derivative
emitter material
emitting diode
organic light
light emitting
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CN102633709A (en
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裴坚
雷霆
莫尧安
孙杰
李孟庭
吴长晏
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Peking University
AU Optronics Suzhou Corp Ltd
AU Optronics Corp
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Peking University
AU Optronics Suzhou Corp Ltd
AU Optronics Corp
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Abstract

The invention discloses a main luminophor material and an organic light emitting diode containing the same. The main luminophor material is a carbazole derivate in structure of a chemical formula (I) shown in the description, wherein R1 and R2 can be independently R4 or X refers to a sulfide bond, a sulfoxide bond or a sulfone bond, Y refers to carbon or nitrogen, R4 refers to hydrogen, fluorine, chlorine, bromine, iodine, alkyl of C1-C30 and alkanol group or aryl substituted group of C1-C30, n refers to integer ranging from 0 to 2, and R3 is shown in the description, R5 refers to hydrogen or is shown in the description, R6 refers to R4 or is shown in the description.

Description

Host emitter material and the Organic Light Emitting Diode that contains host emitter material
Technical field
The invention relates to a kind of host emitter material, particularly about a kind of phosphorescence host emitter material.
Background technology
Organic Light Emitting Diode (organic light-emitting diode, OLED) belong to two (dual-injection) elements that inject of hole (hole) and electronics, wherein hole and electronics inject and are passed to luminescent layer from anode and negative electrode respectively, in luminescent layer, recombinate and produce can be luminous exciton (exciton).For improving luminous efficiency, above-mentioned luminous zone must isolate with electrode surface, to avoid making exciton cancellation (quenching).For this reason, develop the polymeric light-emitting device with multilayered structure, its structure is sequentially respectively anode, hole transport layer (hole-transport layer, HTL), luminescent layer (light-emitting layer, EL), electron transfer layer (electron-transport layer) and negative electrode.
The host emitter material of known Organic Light Emitting Diode (OLED), for example 4,4 '; 4 " two (9H-carbazole-9-yl) benzene (mcp) of-tri-(9-carbazyl) triphenylamines (TcTa) or 1,3-all belongs to preferably host emitter material of cavity transmission ability.But, cavity transmission ability preferably host emitter material, often due to excited triplet state (excited triplet state, T1) energy shortage, makes external quantum efficiency (External Quantum Efficiency, EQE) low, cause luminous efficiency not good.
Summary of the invention
Therefore an aspect of the present invention is to provide host emitter (host) material of a kind of Organic Light Emitting Diode (OLED).Above-mentioned host emitter material is a kind of carbazole (carbazole) derivative, and it has the structure of following chemical formula (I):
Figure GDA0000363999480000011
Wherein R 1with R 2can distinguish independent is R 4or its X is sulfide linkage (sulfur linkage ,-S-), sulfoxide key (sulfoxide linkage ,-SO-) or sulfone key (sulfone linkage ,-SO 2-), Y is carbon or nitrogen, R 4for hydrogen or chlorine, and
R 3for
Figure GDA0000363999480000023
or
Figure GDA0000363999480000024
According to one embodiment of the invention, wherein work as the R of this chemical formula (I) 1for hydrogen or
Figure GDA0000363999480000025
time, its X is sulfoxide key (SO-) or sulfone key (SO 2-), R 4for hydrogen or chlorine, as the R of this chemical formula (I) 2for
Figure GDA0000363999480000026
time, its X is sulfoxide key (SO-) or sulfone key (SO 2-), R 4for hydrogen or chlorine, and work as the R of this chemical formula (I) 3for time, its R 4for hydrogen, the structure of above-mentioned host emitter material is one of the following chemical structure formula:
Figure GDA0000363999480000031
According to another embodiment of the present invention, wherein work as the R of chemical formula (I) 1with R 2for
Figure GDA0000363999480000032
time, its R 4for hydrogen, X is sulfone key (SO 2-), Y is carbon, and works as the R of this chemical formula (I) 3for
Figure GDA0000363999480000033
time, the structure of above-mentioned host emitter material is the following chemical structure formula:
Figure GDA0000363999480000041
According to one embodiment of the invention, wherein work as the R of this chemical formula (I) 1with R 2for R 4time, R 4for hydrogen or chlorine, and work as the R of this chemical formula (I) 3for
Figure GDA0000363999480000042
r 4during for hydrogen or chlorine, the structure of above-mentioned host emitter material is following chemical formula V:
According to another embodiment of the present invention, wherein work as the R of chemical formula V 4during for hydrogen, the structure of above-mentioned host emitter material is the following chemical structure formula:
Figure GDA0000363999480000051
According to still another embodiment of the invention, the excited triplet state energy rank of above-mentioned host emitter material value (excited triplet state, T 1) for being greater than 2.8 electron-volts (eV).
Another aspect of the present invention is to provide a kind of Organic Light Emitting Diode (OLED).Its structure comprise the first electrode and with respect to the second electrode of this first electrode, be disposed at hole transmission layer between the first electrode and the second electrode and with respect to the electron transfer layer of hole transmission layer and be disposed at hole transmission layer and electron transfer layer between luminescent layer, above-mentioned luminescent layer comprises host emitter material and guest emitter material, and wherein host emitter material is as chemical formula (I) or (V).
According to one embodiment of the invention, the first electrode of above-mentioned Organic Light Emitting Diode and the second electrode, be selected from respectively transparency electrode or reflecting electrode one of them.Wherein transparency electrode for example can be tin indium oxide (ITO), and reflecting electrode for example can be aluminium-lithium fluoride (Al/LiF).
According to another embodiment of the present invention, the hole transmission layer of above-mentioned Organic Light Emitting Diode is hole mobile material, for example, can be 4,4 ', 4 "-tri-(9-carbazyl) triphenylamines (TcTa).
According to still another embodiment of the invention, the electron transfer layer of above-mentioned Organic Light Emitting Diode is electron transport material, for example can be three (oxine) aluminium (Alq3) or 4,7-phenylbenzene-1,10-o-phenanthroline (Bphen).
According to an embodiment more of the present invention, the guest emitter of above-mentioned Organic Light Emitting Diode is two (3, 5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III) is (FIrpic), two (3, 5-difluorophenyl pyridyl) four (1-pyrazolyl) boric acid iridium (III) are (FIr6), two (3, 5-difluorophenyl pyridyl)-5-(2-pyridyl)-1 hydrogen-tetrazolium iridium (III) is (FIrN4), two (3, 5-difluorophenyl pyridyl)-3-(trifluoromethyl)-5-(2-pyridyl)-1, 2, 4-triazole iridium (III) (FIrtaz), three (2-phenylpyridyl) iridium (III) (Irppy3), two (2-phenylquinoline bases) (methyl ethyl diketone) iridium (III) (PQIr), or three (1-phenyl isoquinolin quinoline base) iridium (III) (Irpiq).
According to one embodiment of the invention, the weight concentration percentage of above-mentioned host emitter material and above-mentioned guest emitter material is more than 4 times, and the weight concentration per-cent of guest emitter material is not 0.
According to another embodiment of the present invention, the external quantum efficiency of the main light emission layer of above-mentioned Organic Light Emitting Diode (external quantum efficiency, EQE) is more than 13.
Accompanying drawing explanation
Fig. 1 is absorption or the excitation spectrum of carbazole derivative Cbz1, wherein transverse axis is that wavelength (nm) and the longitudinal axis are stdn intensity, the wherein maximum absorption wavelength of carbazole derivative Cbz1 (x-), room temperature excitation wavelength (△-), and temperature 77K maximum excitation wavelength (-);
Fig. 2 is absorption or the excitation spectrum of carbazole derivative Cbz2, wherein transverse axis is that wavelength (nm) and the longitudinal axis are stdn intensity, the wherein maximum absorption wavelength of carbazole derivative Cbz2 (x-), room temperature excitation wavelength (△-), and temperature 77K maximum excitation wavelength (-);
Fig. 3 is the structural representation illustrating according to the Organic Light Emitting Diode 100 of the present invention's one aspect;
Wherein, main element nomenclature:
100: 110: the first electrodes of Organic Light Emitting Diode
120: the second electrodes 130: hole transmission layer
140: electron transfer layer 150: luminescent layer.
Embodiment
Below will and describe the clear spirit of the present invention of setting forth in detail with diagram, but persond having ordinary knowledge in the technical field of the present invention is after understanding embodiments of the present invention, can, by the technology of model shown in the present, change and modify, its result does not depart from spirit of the present invention and scope.
Host emitter material
An aspect of the present invention provides a kind of host emitter material and manufacture method thereof of Organic Light Emitting Diode, and above-mentioned host emitter material is a kind of carbazole derivative.The structure of above-mentioned carbazole derivative is as shown in following chemical formula (I):
Figure GDA0000363999480000061
Wherein R 1with R 2can distinguish independent is R 4or its X is sulfide linkage (sulfur linkage ,-S-), sulfoxide key (sulfoxide linkage ,-SO-) or sulfone key (sulfone linkage ,-SO 2-), Y is carbon or nitrogen, R 4for hydrogen or chlorine, and
R 3for or
Figure GDA0000363999480000074
Embodiment 1: carbazole derivative Cbz1
At this, provide carbazole derivative Cbz1 and manufacture method thereof, and carbazole derivative Cbz1 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbz1 is as shown in following chemical formula:
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative Cbz1 comprises carbazole, single halogenating reaction, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbz1.
Figure GDA0000363999480000081
In N-phenylating reaction (asking for an interview the 1st flow process), at (the K of salt of wormwood 2cO 3) weak base condition under, allow carbazole and iodobenzene carry out two molecule nucleophilic substitution reactions, form the phenylating product (1) on nitrogen (N) position with phenyl.
The proton nmr spectra of phenylating product (1) ( 1h NMR, 300MHz, CDCl 3): 8.16-8.13 (m, 2H), 7.63-7.54 (m, 2H), 7.51-7.40 (m, 5H) and 7.38-7.24 (m, 4H).
Figure GDA0000363999480000082
In single halogenating reaction (asking for an interview the 2nd flow process), under the effect of N-bromo-succinimide (NBS), make phenylating product (1) carry out single bromine substitution reaction, single halogenated products (2) that to form No. 3 positions be bromine.
In aromatic thiol substitution reaction (asking for an interview the 3rd flow process), under the effect of n-Butyl Lithium (n-BuLi), allow single halogenated products (2) and Diphenyl disulfide ether carry out substitution reaction, the first thioether product (3) that to form No. 3 positions be thioether group.
In sulfide linkage oxidizing reaction (asking for an interview the 4th flow process), under the effect of metachloroperbenzoic acid, allow the sulfide linkage of the first thioether product (3) carry out oxidizing reaction, form carbazole derivative Cbz1.
The proton nmr spectra of carbazole derivative Cbz1 ( 1h NMR, 400MHz, DMSO): 9.0 (d, 1H), 8.5 (d, 1H), 8.01 (q, 2H), 7.97 (d, 1H), 7.7 (t, 3H), 7.56 (m, 7H) and 7.37 (q, 2H).
Fig. 1 is absorption or the excitation spectrum of carbazole derivative Cbz1, and wherein transverse axis is that wavelength (nm) and the longitudinal axis are stdn intensity.As shown in Figure 1, the maximum absorption wavelength of carbazole derivative Cbz1 (x-) is 283 and 325 nanometers, and room temperature excitation wavelength (△-) is 350 and 367 nanometers, and temperature 77K maximum excitation wavelength (-) is 408 and 436 nanometers.
In addition, from the curve distribution of Fig. 1, the absorption spectrum (x-) of carbazole derivative Cbz1 is less than 3% with the overlapping rate of room temperature excitation spectrum (△-), and the overlapping rate convergence 0% of absorption spectrum (x-) and temperature 77K maximum excitation wavelength (-).The above results represents, due to the absorption spectrum of carbazole derivative Cbz1 and the overlapping rate of emission spectrum extremely low, therefore can effectively transfer absorb light to exciting light.
Embodiment 2: carbazole derivative Cbz2
At this, provide carbazole derivative Cbz2 and manufacture method thereof, and carbazole derivative Cbz2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbz2 is as shown in following chemical formula:
Figure GDA0000363999480000101
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative Cbz2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbz2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.
Figure GDA0000363999480000102
In two halogenation flow processs (asking for an interview the 5th flow process), at acetic acid (CH 3cOOH), under acidic conditions, make phenylating product (1) and bromine water (Br 2) carry out bromination reaction, form No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.
The proton nmr spectra of first pair of halogenated products (4) ( 1h NMR, 300MHz, CDCl 3): 8.20 (d, 2H), 7.64-7.59 (m, 2H), 7.52-7.48 (m, 5H), 7.27 (s, 1H) and 7.25 (s, 1H).
Figure GDA0000363999480000103
In aromatic thiol base substitution reaction (asking for an interview the 6th flow process), under the effect of n-Butyl Lithium (n-BuLi), allow first pair of halogenated products (4) and Diphenyl disulfide ether (Ph 2s 2) carry out substitution reaction, form No. 3 and the second thioether product (5) that No. 6 positions are thioether group.
The proton nmr spectra of the second thioether product (5) ( 1h NMR, 300MHz, CDCl 3): 8.26 (d, 2H), 7.66-7.50 (m, 10H), 7.41-7.38 (m, 2H), 7.27-7.18 (m, 5H) and 7.16-7.11 (m, 2H); ESI-MS:[M+1] +=460.
Figure GDA0000363999480000111
In sulfide linkage oxidizing reaction (asking for an interview the 7th flow process), (mole ratio m-CPBA:(5)=4:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of the second thioether product (5) carry out oxidizing reaction, form carbazole derivative Cbz2.
The proton nmr spectra of carbazole derivative Cbz2 ( 1h NMR, 400MHz, DMSO): 9.32 (d, 2H), 8.04 (m, 6H), 7.64 (m, 11H) and 7.48 (d, 2H).
Fig. 2 is absorption or the excitation spectrum of carbazole derivative Cbz2, and wherein transverse axis is that wavelength (nm) and the longitudinal axis are stdn intensity.As shown in Figure 2, the maximum absorption wavelength of carbazole derivative Cbz2 (x-) is 284 and 312 nanometers, and room temperature excitation wavelength (△-) is 349 and 367 nanometers, and temperature 77K maximum excitation wavelength (-) is 403 and 435 nanometers.
In addition, from the curve distribution of Fig. 2, the absorption spectrum (x-) of carbazole derivative Cbz2 is less than 1% with the overlapping rate of room temperature excitation spectrum (△-), and the overlapping rate convergence 0% of absorption spectrum (x-) and temperature 77K maximum excitation wavelength (-).The above results represents, due to the absorption spectrum of carbazole derivative Cbz2 and the overlapping rate of emission spectrum extremely low, therefore can effectively transfer absorb light to exciting light.
Embodiment 3: carbazole derivative Cbbso2
At this, provide carbazole derivative Cbbso2 and manufacture method thereof, and carbazole derivative Cbbso2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbbso2 is as shown in following chemical formula:
Figure GDA0000363999480000112
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative Cbbso2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbbso2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.In two halogenation flow processs, by the method as described in aforementioned the 5th flow process, obtain No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.In the substitution reaction of aromatic thiol base, by the method as described in aforementioned the 6th flow process, obtain No. 3 and the second thioether product (5) that No. 6 positions are thioether group.
In sulfide linkage oxidizing reaction (asking for an interview the 8th flow process), (mole ratio m-CPBA:(5)=2:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of the second thioether product (5) carry out oxidizing reaction, form carbazole derivative Cbbso2.
The proton nmr spectra of carbazole derivative Cbbso2 ( 1h NMR, 300MHz, CDCl 3): 8.52 (t, 2H), 7.71-7.57 (m, 10H) and 7.51-7.37 (m, 9H); ESI-MS:[M+1] +=514.
Embodiment 4: carbazole derivative Cbps2
At this, provide carbazole derivative Cbps2 and manufacture method thereof, and carbazole derivative Cbps2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbps2 is as shown in following chemical formula:
Figure GDA0000363999480000122
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative Cbps2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbps2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.In two halogenation flow processs, by the method as described in aforementioned the 5th flow process, obtain No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.
In aromatic thiol base substitution reaction (asking for an interview the 9th flow process), under the effect of n-Butyl Lithium (n-BuLi), allow first pair of halogenated products (4) and bipyridyl disulfide carry out substitution reaction, form No. 3 and trithioether product (6) that No. 6 positions are thioether group.
The proton nmr spectra of trithioether product (6) ( 1h NMR, 300MHz, CDCl 3): 8.4 (d, 4H), 7.66 (d, 2H), 7.63-7.51 (m, 5H), 7.29 (d, 2H), 7.42-7.37 (m, 2H), 7.70-6.93 (m, 2H) and 6.83-6.80 (t, 2H); ESI-MS:[M+1] +=463.
In sulfide linkage oxidizing reaction (asking for an interview the 10th flow process), (mole ratio m-CPBA:(6)=4:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of trithioether product (6) carry out oxidizing reaction, form carbazole derivative Cbps2.
The proton nmr spectra of carbazole derivative Cbps2 ( 1h NMR, 300MHz, CDCl 3): 8.91 (d, 2H), 8.70 (d, 2H), 8.31 (d, 2H), 8.20 (dd, 2H), 7.96 (m, 2H), 7.68-7.55 (m, 4H) and 7.42-7.39 (m, 5H); ESI-MS:[M+1] +=526.
Embodiment 5: carbazole derivative Cbpso2
At this, provide carbazole derivative Cbpso2 and manufacture method thereof, and carbazole derivative Cbpso2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbpso2 is as shown in following chemical formula:
Figure GDA0000363999480000141
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative Cbpso2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbpso2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.In two halogenation flow processs, by the method as described in aforementioned the 5th flow process, obtain No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.In the substitution reaction of aromatic thiol base, by the method as described in aforementioned the 9th flow process, obtain No. 3 and trithioether product (6) that No. 6 positions are thioether group.
In sulfide linkage oxidizing reaction (asking for an interview the 11st flow process), (mole ratio m-CPBA:(6)=2:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of trithioether product (6) carry out oxidizing reaction, form carbazole derivative Cbpso2.
The proton nmr spectra of carbazole derivative Cbpso2 ( 1h NMR, 300MHz, CDCl 3): 8.60 (dd, 2H), 8.54-8.50 (m, 2H), 8.18-8.12 (m, 2H), 7.91-7.88 (m, 2H), 7.82-7.78 (m, 2H), 7.60-7.44 (m, 3H), 7.42-7.36 (m, 4H) and 7.30-7.25 (m, 2H); ESI-MS:[M+1] +=494.
Embodiment 6: carbazole derivative CbbCls2
At this, provide carbazole derivative CbbCls2 and manufacture method thereof, and carbazole derivative CbbCls2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative CbbCls2 is as shown in following chemical formula:
Figure GDA0000363999480000151
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative CbbCls2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative CbbCls2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.In two halogenation flow processs, by the method as described in aforementioned the 5th flow process, obtain No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.
Figure GDA0000363999480000152
In aromatic thiol base substitution reaction (asking for an interview the 12nd flow process), under the effect of n-Butyl Lithium (n-BuLi), allow first pair of halogenated products (4) and two rubigan disulfides carry out substitution reaction, form No. 3 and the 4th thioether product (7) that No. 6 positions are thioether group.
The proton nmr spectra of the 4th thioether product (7) ( 1h NMR, 300MHz, CDCl 3): 7.67-7.62 (m, 2H), 7.57-7.50 (m, 5H), 7.40 (d, 2H) and 7.21-7.11 (m, 8H); ESI-MS:[M+1] +=528.
Figure GDA0000363999480000161
In sulfide linkage oxidizing reaction (asking for an interview the 13rd flow process), (mole ratio m-CPBA:(7)=6:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of the 4th thioether product (7) carry out oxidizing reaction, form carbazole derivative CbbCls2.
The proton nmr spectra of carbazole derivative CbbCls2 ( 1h NMR, 300MHz, CDCl 3): 8.80 (d, 2H), 8.02-7.93 (m, 6H), 7.67-7.58 (m, 3H) and 7.51-7.41 (m, 8H); ESI-MS:[M+1] +=592.
Embodiment 7: carbazole derivative CbbClso2
At this, provide carbazole derivative CbbClso2 and manufacture method thereof, and carbazole derivative CbbClso2 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative CbbClso2 is as shown in following chemical formula:
Figure GDA0000363999480000162
According to one embodiment of the invention, the N-phenylating reaction that the manufacture method of carbazole derivative CbbClso2 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative CbbClso2.
In the reaction of N-phenylating, by the method as described in aforementioned the 1st flow process, obtain having on nitrogen (N) position the phenylating product (1) of phenyl.In two halogenation flow processs, by the method as described in aforementioned the 5th flow process, obtain No. 3 and first pair of halogenated products (4) that No. 6 positions are bromine.In the substitution reaction of aromatic thiol base, by the method as described in aforementioned the 12nd flow process, obtain No. 3 and the 4th thioether product (7) that No. 6 positions are thioether group.
Figure GDA0000363999480000171
In sulfide linkage oxidizing reaction (asking for an interview the 14th flow process), (mole ratio m-CPBA:(7)=3:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of the 4th thioether product (7) carry out oxidizing reaction, form carbazole derivative CbbClso2.
The proton nmr spectra of carbazole derivative CbbClso2 ( 1h NMR, 300MHz, CDCl 3): 8.81 (d, 2H), 8.49-7.51 (m, 6H), 7.49-7.41 (m, 3H) and 7.39-7.37 (m, 8H); ESI-MS:[M+1] +=560.
Table 1
Figure GDA0000363999480000172
Figure GDA0000363999480000181
Table 1 is maximum absorption wavelength, maximum excitation wavelength and excited triplet state energy rank value (excited triplet state, the T of above-mentioned 7 kinds of carbazole derivative 1).As shown in Table 1, the gap of the maximum absorption wavelength of above-mentioned 7 kinds of carbazole derivative and maximum excitation wavelength is 28-95 nanometer, and T 1value is 3.00-3.05 electron-volt (eV).
Wherein, as the T of main light emission material 1when value is greater than 2.8 electron-volts, the luminous efficiency of this main light emission material is better.Compared to the T of known host emitter material TcTa 1value is 2.7, the T of above-mentioned carbazole derivative 1value is all greater than 2.8 electron-volts, therefore has preferably luminous efficiency.
Embodiment 8: carbazole derivative Cbz3
At this, provide carbazole derivative Cbz3 and manufacture method thereof, and carbazole derivative Cbz3 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative Cbz3 is as shown in following chemical formula:
According to one embodiment of the invention, the N-biphenyl glycosylation reaction that the manufacture method of carbazole derivative Cbz3 comprises carbazole, two halogenating reactions, the substitution reaction of aromatic thiol base and the sulfide linkage oxidizing reaction of carbazole.By above-mentioned reaction process, obtain carbazole derivative Cbz3.
Figure GDA0000363999480000191
In N-biphenyl glycosylation reaction (asking for an interview the 15th flow process), at (the K of salt of wormwood 2cO 3) weak base condition under, allow carbazole and bromobenzene carry out two molecule nucleophilic substitution reactions, form the xenyl product (8) on nitrogen (N) position with xenyl.
The proton nmr spectra of xenyl product (8) ( 1h NMR, 300MHz, CDCl 3): 8.16 (d, 2H, J=7.5Hz), 7.83 (d, 2H, J=8.7Hz), 7.68 (dd, 4H, J=9Hz, 12Hz) and 7.54-7.33 (m, 9H); ESI-MS:[M+1] +=319.
Figure GDA0000363999480000192
In two halogenating reactions (asking for an interview the 16th flow process), at acetic acid (CH 3cOOH), under acidic conditions, make xenyl product (8) and bromine water (Br 2) carry out bromination reaction, form No. 3 and second pair of halogenated products (9) that No. 6 positions are bromine.
The proton nmr spectra of second pair of halogenated products (9) ( 1h NMR, 300MHz, CDCl 3): 8.20 (d, 2H, J=1.8Hz), 7.81 (d, 2H, J=8.1Hz), 7.67 (d, 2H, J=7.8Hz) and 7.57-7.29 (m, 9H); ESI-MS:[M+1] +=477.
Figure GDA0000363999480000201
In aromatic thiol base substitution reaction (asking for an interview the 17th flow process), under the effect of n-Butyl Lithium (n-BuLi), allow second pair of halogenated products (9) and Diphenyl disulfide ether (Ph 2s 2) carry out substitution reaction, form No. 3 and the 5th thioether product (10) that No. 6 positions are thioether group.
The proton nmr spectra of the 5th thioether product (10) ( 1h NMR, 300MHz, CDCl 3): 8.26 (d, 2H, J=1.5Hz), 7.84 (d, 2H, J=6.9Hz), 7.68-7.42 (m, 9H) and 7.24-7.12 (m, 10H); ESI-MS:[M+1] +=535.
Figure GDA0000363999480000202
In sulfide linkage oxidizing reaction (asking for an interview the 18th flow process), (mole ratio m-CPBA:(10)=4:1 under the effect of metachloroperbenzoic acid (m-CPBA)), allow the sulfide linkage of the 5th thioether product (10) carry out oxidizing reaction, form carbazole derivative Cbz3.
The proton nmr spectra of carbazole derivative Cbz3 ( 1h NMR, 300MHz, CDCl 3): 8.82 (d, 2H, J=1.2Hz), 8.06-7.85 (m, 9H), 7.38 (d, 2H, J=8.4Hz), 7.66 (d, 2H, J=8.4Hz) and 7.58-7.42 (m, 10H); ESI-MS:[M+1] +=599.
Embodiment 9: carbazole derivative FYL-B41
At this, provide carbazole derivative FYL-B41 and manufacture method thereof, and carbazole derivative FYL-B41 can be as the host emitter material of Organic Light Emitting Diode.The structure of above-mentioned carbazole derivative FYL-B41 is as shown in following chemical formula:
According to one embodiment of the invention, the manufacture method of carbazole derivative FYL-B41 comprises sulphonamide substitution reaction and two carbazole substitution reactions.By above-mentioned reaction process, obtain carbazole derivative FYL-B41.
Figure GDA0000363999480000212
In sulphonamide substitution reaction (asking for an interview the 19th flow process), at triethylamine (Et 3n) under alkaline condition, allow two (4 '-bromophenyl) the second diketone of 1,2-and sulphonamide (
Figure GDA0000363999480000213
) carry out substitution reaction, form the sulphonamide substitution product (11) with thiadiazoles group.
The proton nmr spectra of sulphonamide substitution product (11) ( 1h NMR, 300MHz, CDCl 3): 7.64 (d, 4H, J=6.0Hz) and 7.44 (d, 4H, J=8.7Hz); ESI-MS:[M+1] +=428.
Figure GDA0000363999480000221
In two carbazole substitution reactions (asking for an interview the 20th flow process), under the catalysis of cupric iodide (CuI), allow sulphonamide substitution product (11) and carbazole carry out substitution reaction (mole ratio carbazole: (11)=2.5:1), form the carbazole derivative FYL-B41 with two carbazole groups.
The proton nmr spectra of carbazole derivative FYL-B41 ( 1h NMR, 300MHz, CDCl 3): 8.14 (dd, 4H, J=1.8Hz, 7.2Hz), 7.66 (dd, 4H, J=1.8Hz, 7.2Hz), 7.50-7.44 (m, 4H), 7.42-7.36 (m, 4H), 7.32-7.28 (m, 4H) and 7.11-7.06 (m, 4H); ESI-MS:[M+1] +=600.
Carbazole derivative is in the application of Organic Light Emitting Diode
Because above-mentioned carbazole derivative can be as the host emitter material of Organic Light Emitting Diode, therefore apply in the following embodiments above-mentioned carbazole derivative and manufacture Organic Light Emitting Diode.
The structure of above-mentioned Organic Light Emitting Diode as shown in Figure 3.In Fig. 3, the structure of Organic Light Emitting Diode 100 comprise the first electrode 110 and with respect to the second electrode 120 of this first electrode 110, be disposed at hole transmission layer 130 between the first electrode 110 and the second electrode 120 and with respect to the electron transfer layer 140 of hole transmission layer 130 and be disposed at hole transmission layer 130 and electron transfer layer 140 between luminescent layer 150.Above-mentioned luminescent layer 150 comprises host emitter material and guest emitter material, and wherein host emitter material can be with above-mentioned carbazole derivative.
Embodiment 10
Embodiment 10 provides a kind of Organic Light Emitting Diode, and its structure as shown in Figure 3.Wherein the first electrode 110 is tin indium oxide (ITO) base material, the second electrode 120 is aluminium-lithium fluoride (Al/LiF), hole transmission layer 130 is hole mobile material AUS HIL and 4,4 '; 4 "-tri-(9-carbazyl) triphenylamines (TcTa), electron transfer layer 140 is three (oxine) aluminium (Alq 3), and luminescent layer 150 is that carbazole derivative Cbz1 (FIrpic) mixes with two (3,5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III).
Wherein the host emitter material of luminescent layer composition is carbazole derivative Cbz1, and guest emitter material is that two (3,5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III) (FIrpic).And the weight concentration percentage of host emitter material and guest emitter material is more than 4 times, and the weight concentration per-cent of guest emitter material is not equal in fact 0.
Embodiment 11
Embodiment 11 provides a kind of Organic Light Emitting Diode, and its structure as shown in Figure 3.Wherein the first electrode 110 is tin indium oxide (ITO) base material, the second electrode 120 is aluminium-lithium fluoride (Al/LiF), hole transmission layer 130 is hole mobile material AUS HIL and 4,4 '; 4 "-tri-(9-carbazyl) triphenylamines (TcTa), electron transfer layer 140 is three (oxine) aluminium (Alq 3), and luminescent layer 150 is that carbazole derivative Cbz2 (FIrpic) mixes with two (3,5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III).
Wherein the host emitter material of luminescent layer composition is carbazole derivative Cbz1, and guest emitter material is that two (3,5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III) (FIrpic).And the weight concentration percentage of host emitter material and guest emitter material is more than 4 times, and the weight concentration per-cent of guest emitter material is not equal in fact 0.
Table 2
Table 2 is more different host emitter materials, the luminous intensity on Organic Light Emitting Diode (OLED) and the impact of external quantum efficiency.Wherein embodiment 10 and embodiment 11 are respectively take Cbz1 and Cbz2 as host emitter material; And comparative example is take known TcTa as host emitter material.As shown in Table 2, compared to comparative example, all obvious better (≤26.5cd/A of the luminous intensity of embodiment 10 and embodiment 11), and also obvious better (≤13% of external quantum efficiency (External Quantum Efficiency, EQE)).
The host emitter material that an aspect of the present invention provides has preferably cavity transmission ability, and because its T 1value is greater than 2.8 electron-volts, promotes external quantum efficiency, and luminous intensity is obviously increased.Therefore, for known technology problem, above-mentioned host emitter material is a better solution, and can directly apply to the phosphorescence luminescent layer of Organic Light Emitting Diode.
Preferred forms of the present invention is to disclose as mentioned above, but cited manufacture method is not limited to embodiments of the invention.Any skill person of the habit in the technical field of the invention, when not departing from spirit of the present invention and scope, can carry out various modifications or conversion.So the scope that protection scope of the present invention defines when following appending claims is as the criterion.

Claims (4)

1. a host emitter material, the structure of this host emitter material is one of the following chemical structure formula:
Figure FDA0000463553300000011
2. an Organic Light Emitting Diode, comprises:
One first electrode and second electrode with respect to this first electrode;
One hole transmission layer and an electron transfer layer with respect to this hole transmission layer, wherein this hole transmission layer and this electron transfer layer are disposed between this first electrode and this second electrode; And
One luminescent layer, is disposed between this hole transmission layer and this electron transfer layer, and this luminescent layer comprises a host emitter material and a guest emitter material, and this host emitter material as claimed in claim 1.
3. Organic Light Emitting Diode as claimed in claim 2, wherein this guest emitter is two (3, 5-difluorophenyl pyridyl)-(2-carboxyl pyridine base) iridium (III), two (3, 5-difluorophenyl pyridyl) four (1-pyrazolyl) boric acid iridium (III), two (3, 5-difluorophenyl pyridyl)-5-(2-pyridyl)-1 hydrogen-tetrazolium iridium (III), two (3, 5-difluorophenyl pyridyl)-3-(trifluoromethyl)-5-(2-pyridyl)-1, 2, 4-triazole iridium (III), three (2-phenylpyridyl) iridium (III), two (2-phenylquinoline base) (methyl ethyl diketone) iridium (III), or three (1-phenyl isoquinolin quinoline base) iridium (III).
4. Organic Light Emitting Diode as claimed in claim 3, wherein the weight concentration percentage of this host emitter material and this guest emitter material is more than 4 times, and the weight concentration per-cent of this guest emitter material is not 0.
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