CN109928962A - It is a kind of using carbazole as the compound of core, preparation method and its application on organic electroluminescence device - Google Patents
It is a kind of using carbazole as the compound of core, preparation method and its application on organic electroluminescence device Download PDFInfo
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Abstract
The invention belongs to technical field of semiconductors more particularly to a kind of using carbazole as the compound of core, preparation method and its application on organic electroluminescence device, shown in the structure of organic compound provided by the invention such as general formula (1):Application the invention also discloses the preparation method of above compound and its on organic electroluminescence device, compound provided by the invention glass transition temperature with higher and molecule thermal stability, suitable HOMO and lumo energy, higher Eg, optimized by device architecture, can effectively promote the photoelectric properties of OLED device and the service life of OLED device.
Description
Technical field
The invention belongs to technical field of semiconductors more particularly to it is a kind of using carbazole as the compound of core, preparation method and
Its application on organic electroluminescence device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.
OLED luminescent device including electrode material film layer and is clipped between Different electrodes film layer like the structure of sandwich
Organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together.
OLED luminescent device is as current device, when applying voltage to its two end electrodes, and passes through electric field action organic layer functional material
When positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity
Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency and use of OLED device
The performances such as service life also need further to be promoted.
Proposing high performance research to OLED luminescent device at present includes: the driving voltage for reducing device, the hair for improving device
Light efficiency, the service life for improving device etc..In order to realize OLED device performance continuous promotion, not only need from OLED device
The innovation of part structure and manufacture craft is constantly studied and is innovated with greater need for oled light sulfate ferroelectric functional material, formulates out higher performance
OLED functional material.
Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes from purposes, and respectively charge injects
Transmission material and luminescent material.Further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking
Luminescent material, can also be divided into main body luminescent material and doping material by material, hole injection transmission material and hole barrier materials
Material.
In order to make high performance OLED luminescent device, it is desirable that various organic functional materials have good photoelectric properties,
For example, as charge transport materials, it is desirable that have good carrier mobility, high-vitrification conversion temperature etc., as luminous
The material of main part of layer has good bipolarity, HOMO/LUMO energy rank appropriate etc..
The oled light sulfate ferroelectric functional material film layer for constituting OLED device includes at least two layers or more structure, applies in industry
OLED device structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron-transport
A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is injected including at least hole
Material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and various
The characteristics of property.In addition, used photoelectric functional material has stronger choosing for the collocation of the OLED device of different structure
Selecting property, performance of the identical material in different structure device may also be completely totally different.
Therefore, for the industry application requirement of current OLED device and the different function film layer of OLED device, device
Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the higher OLED functional material of performance or combination of materials, is just able to achieve the height of device
Efficiency, the overall characteristic of long-life and low-voltage.For current OLED shows the actual demand of Lighting Industry, OLED at present
The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance
Functional material is particularly important.
Summary of the invention
In order to solve the above-mentioned technical problem the present invention provides a kind of with the compound of carbazole core and its in organic electroluminescence hair
It is applied on optical device, the compounds of this invention contains carbazole structure, glass transition temperature with higher and molecule thermal stability, properly
HOMO and lumo energy, higher Eg optimized by device architecture, can effectively promote the photoelectric properties and OLED of OLED device
The service life of device.
The technical scheme to solve the above technical problems is that a kind of using carbazole as the compound of core, the chemical combination
Shown in the structure of object such as general formula (1):
Wherein, Ar1、Ar2、Ar3Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one
Or one of multiple heteroatomic substituted or unsubstituted 5~60 yuan of heteroarylidenes, the hetero atom be nitrogen, oxygen or sulphur,
Ar1、Ar2、Ar3It can be identical or different；
In general formula (1), R1、R2、R3Independently be expressed as structure shown in hydrogen atom or general formula (2), R1、R2、R3It can
With identical or different, and R1、R2、R3It is not simultaneously hydrogen atom；
Wherein, X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution
One of the imido grpup that substituted alkylidene, alkyl-substituted imido grpup or aryl replaces.
In general formula (1), Ar1、Ar2、Ar3Independently be expressed as singly-bound, phenylene, biphenylene, naphthylene or sub- pyrrole
One of piperidinyl.
Further, the concrete structure formula of the compound are as follows:
In it is any one
Kind.
The present invention provides a kind of using carbazole as the preparation method of the compound of core, comprising:
Reaction equation using preparation method 1 is as follows:
Specific preparation process the following steps are included:
1) raw material A is added in toluene with raw material B and is dissolved, wherein the toluene dosage is that every gram of raw material A uses 30
The molar ratio of~50ml toluene, the raw material A and raw material B are 1:(1.0~1.5)；
2) Pd (PPh is added into the reaction system of step 1)3)4And sodium carbonate, wherein the Pd (PPh3)4With raw material A
Molar ratio be (0.005~0.01): 1, the molar ratio of the sodium carbonate and raw material A is (1.5~3.0): 1, obtain mixing molten
Liquid；
3) it under nitrogen protection, by mixed solution obtained in step 2) in 95~110 DEG C, reacts 10~24 hours, from
It is so cooled to room temperature, and filtering reacting solution, filtrate carries out vacuum rotary steam, crosses neutral silica gel column, obtains intermediate C；
4) intermediate C obtained in step 3) and raw material D is added in toluene and is dissolved, wherein the toluene dosage
30-50ml toluene is used for every gram of intermediate C, the molar ratio of the intermediate C and raw material D is 1:(1.0~1.5)；
5) Pd (PPh is added into the reaction system of step 4)3)4And sodium carbonate, wherein the Pd (PPh3)4With intermediate
The molar ratio of C is (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate C are (1.5~3.0): and 1, it is mixed
Solution；
6) it under nitrogen protection, by mixed solution obtained in step 5) in 95~110 DEG C, reacts 10~24 hours, from
It is so cooled to room temperature, and filtering reacting solution, filtrate carries out vacuum rotary steam, crosses neutral silica gel column, obtains intermediate E.
7) intermediate E is added in toluene with raw material F and is dissolved, wherein the toluene dosage is that every gram of intermediate E uses 30
The molar ratio of~50ml toluene, the intermediate E and raw material F are 1:(1.0~1.5)；
8) Pd is added into the reaction system in step 7)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide；The Pd2
(dba)3It is (0.005~0.01) with the molar ratio of intermediate E: 1, the molar ratio of the tri-tert-butylphosphine and intermediate E is
(0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate E is (1.5~3.0): 1, obtain mixed liquor；
9) under the protection of inert gas, by mixed solution obtained in step 8) under the conditions of 95~110 DEG C of temperature
Reaction 10~for 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotate to solvent-free, cross neutral silica gel column, obtain
Target product 1；
Reaction equation using preparation method 2 is as follows:
Specific preparation process the following steps are included:
1) raw material G and raw material F is added in toluene and is dissolved, wherein the toluene dosage is that every gram of raw material G uses 30-
The molar ratio of 50ml toluene, the middle raw material G and raw material F are 1:(1.0~1.5)；
2) Pd is added into the reaction system in step 1)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide；The Pd2
(dba)3It is (0.005~0.01) with the molar ratio of raw material G: 1, the molar ratio of the tri-tert-butylphosphine and raw material G are (0.005
~0.02): 1, the molar ratio of the sodium tert-butoxide and raw material G are (1.5~3.0): 1, obtain mixed solution；
3) under the protection of inert gas, by mixed solution obtained in step 2) under the conditions of 95~110 DEG C of temperature
Reaction 10~for 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotate to solvent-free, cross neutral silica gel column, obtain
Intermediate H；
4) intermediate H obtained in step 3) and raw material B is added in toluene and is dissolved, wherein the toluene dosage is every
Gram intermediate H uses 30-50ml toluene, and the molar ratio of the intermediate H and raw material B are 1:(1.0~1.5)；
5) Pd (PPh is added into step 4) reaction system3)4And sodium carbonate, wherein the Pd (PPh3)4With intermediate H
Molar ratio be (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate H are (1.5~3.0): 1, mixed
Solution；
6) it under nitrogen protection, by mixed solution obtained in step 5) in 95~110 DEG C, reacts 10~24 hours, from
It is so cooled to room temperature, and filtering reacting solution, filtrate carries out vacuum rotary steam, crosses neutral silica gel column, obtains intermediate compound I；
7) intermediate compound I that step 6) obtains is added in toluene with raw material D and is dissolved, wherein the toluene dosage is every gram
Intermediate compound I uses 30~50ml toluene, and the molar ratio of the intermediate compound I and raw material D are 1:(1.0~1.5)；
8) Pd (PPh is added into step 7) reaction system3)4And sodium carbonate, wherein the Pd (PPh3)4With intermediate compound I
Molar ratio be (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate compound I is (1.5~3.0): 1；
9) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, naturally cools to room
Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain target product 2.
The present invention also provides a kind of applications using carbazole as the compound of core in organic electroluminescence device, this is organic
Electroluminescent device contains above-mentioned a kind of using carbazole as the compound of core including at least one layer of functional layer.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the functional layer is luminescent layer.
Further, the functional layer is hole transmission layer and electronic barrier layer.
The present invention also provides the elements of a kind of illumination or display, including above-mentioned organic electroluminescence device.
The beneficial effects of the present invention are:
1, for the compounds of this invention using carbazole as core, connected symmetrical dendrimer or asymmetrical rigid radical destroy the crystallization of molecule
Property, intermolecular aggtegation is avoided, there is high glass transition temperature, material is in OLED device in application, high film can be kept
Layer stability, improves OLED device service life.
2, the compounds of this invention structure balances electrons and holes more in the distribution of luminescent layer, in appropriate HOMO energy
Under grade, hole injection/transmission performance is improved；Under suitable lumo energy, and play the role of electronic blocking, is promoted and swashed
Combined efficiency of the son in luminescent layer；When light emitting functional layer materials'use as OLED luminescent device, the carbazole collocation present invention
Branch in range can effectively improve exciton utilization rate and high fluorescent radiation efficiency, reduce the efficiency roll-off under high current density,
Device voltage is reduced, current efficiency and the service life of device are improved.
3, for the compounds of this invention centered on carbazole group, 3 branches of connection are radial, after material filming, each
Chain can intersect to form the high film layer of compactness, to reduce leakage current of the material after OLED device application, therefore improve
Device service life.
4, compound of the present invention has good application effect in OLED luminescent device, and preparation method is simple,
With good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；
Fig. 2 is device prepared by the present invention and the efficiency curve diagram that comparative device measures at different temperatures；
Fig. 3 is that the leakage current that device embodiments 1 of the present invention carry out backward voltage with device made by device comparative example 1 is surveyed
Try curve graph.
In attached drawing, parts list represented by the reference numerals are as follows:
1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transmission layer, 5, electronic barrier layer, 6, hair
Photosphere, 7, hole blocking layer/electron transfer layer, 8, electron injecting layer, 9, cathode reflection electrode 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.
Embodiment 1: the synthesis of intermediate E
Ar used below2、Ar3、R2、R3The meaning of equal symbols is identical as specification Summary；
(1) under nitrogen atmosphere, it weighs raw material A and raw material B is dissolved in toluene, Pd (PPh is then added3)4And carbonic acid
Sodium stirs mixture, the mixed solution of above-mentioned reaction is heated to 95~110 DEG C, it is heated to reflux 10~for 24 hours, after reaction,
It is cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains intermediate C；
Wherein, the raw material A and the molar ratio of raw material B are 1:(1.0~1.5), the Pd (PPh3)4With mole of raw material A
Than for (0.005~0.01): 1, the molar ratio of the sodium carbonate and raw material A is (1.5~3.0): 1；
(2) under nitrogen atmosphere, it weighs intermediate C and raw material D is dissolved in toluene, Pd (PPh is then added3)4And carbonic acid
Sodium stirs mixture, the mixed solution of above-mentioned reaction is heated to 95~110 DEG C, it is heated to reflux 10~for 24 hours, after reaction,
It is cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains intermediate E；
Wherein, the molar ratio of the intermediate C and raw material D is 1:(1.0~1.5), the Pd (PPh3)4With intermediate C's
Molar ratio is (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate C are (1.5~3.0): 1；
By taking the synthesis of intermediate E 5 as an example:
(1) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate H1,0.012mol raw material B3 be added,
150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, reflux
Reaction 24 hours samples contact plate, and display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate are subtracted
Pressure revolving (- 0.09MPa, 85 DEG C) crosses neutral silica gel column, obtains target product, HPLC purity 98.7%, yield 70.5%；
(2) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate C1,0.012mol raw material D3 be added,
150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, reflux
Reaction 24 hours samples contact plate, and display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate are subtracted
Pressure revolving (- 0.09MPa, 85 DEG C) crosses neutral silica gel column, obtains target product, HPLC purity 99.2%, yield 69.5%；
Elemental analysis structure (molecular formula C36H23NO): theoretical value C, 89.05；H,4.77；N,2.88；O,3.29；Test
Value: C, 89.04；H,4.79；N,2.85；O,3.32.ESI-MS(m/z)(M+): theoretical value 485.18, measured value are
485.25。
Intermediate E 2 and intermediate E 4 are prepared according to the method for intermediate E 5 is prepared in embodiment 1, raw material correspondence is replaced
It changes using as shown in table 1 below:
Table 1
Embodiment 2: the synthesis of compound 1:
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol intermediate E 1,0.012mol raw material F1,
150ml toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5mol Pd2(dba)3, 5 × 10-5The tertiary fourth of mol tri-
Base phosphine is heated to 105 DEG C, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；It naturally cools to
Room temperature, filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity
99.1%, yield 69.7%；
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.87；H,4.92；N,1.95；O,2.26.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.34。
Embodiment 3: the synthesis of compound 5:
The preparation method is the same as that of Example 1 for compound 5, the difference is that replacing raw material F1 with raw material F2.
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.86；H,4.93；N,1.94；O,2.27.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 4: the synthesis of compound 9:
The preparation method is the same as that of Example 1 for compound 9, the difference is that replacing raw material E1 with raw material E2.
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.88；H,4.92；N,1.94；O,2.26.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 5: the synthesis of compound 11:
The preparation method is the same as that of Example 1 for compound 11, the difference is that replacing raw material E1 with raw material E3.
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.83；H,4.95；N,1.97；O,2.25.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 6: the synthesis of compound 13:
The preparation method is the same as that of Example 1 for compound 5, the difference is that replacing raw material E1 with raw material E4.
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.84；H,4.93；N,1.99；O,2.24.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 7: the synthesis of compound 17:
The preparation method is the same as that of Example 1 for compound 17, the difference is that replacing raw material F1 with raw material F3.
Elemental analysis structure (molecular formula C48H31NO): theoretical value C, 90.40；H,4.90；N,2.20；O,2.51；Test
Value: C, 90.43；H,4.91；N,2.17；O,2.49.ESI-MS(m/z)(M+): theoretical value 637.24, measured value are
637.35。
Embodiment 8: the synthesis of compound 27:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol raw material E3,0.012mol raw material F4,150ml is added
Toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5mol Pd2(dba)3, 5 × 10-5Mol tri-tert-butylphosphine,
105 DEG C are heated to, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature,
Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity
99.4%, yield 64.3%；
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.86；H,4.93；N,1.94；O,2.27.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 9: the synthesis of compound 30:
The preparation method of compound 30 is with embodiment 7, the difference is that replacing raw material E3 with raw material E4.
Elemental analysis structure (molecular formula C54H35NO): theoretical value C, 90.85；H,4.94；N,1.96；O,2.24；Test
Value: C, 90.87；H,4.92；N,1.94；O,2.27.ESI-MS(m/z)(M+): theoretical value 713.27, measured value are
713.35。
Embodiment 10: the synthesis of compound 51:
The preparation method is the same as that of Example 1 for compound 5, the difference is that replacing raw material F1 with raw material F5.
Elemental analysis structure (molecular formula C57H41N): theoretical value C, 92.52；H,5.59；N,1.89；Test value: C,
92.55；H,5.58；N,1.91.ESI-MS(m/z)(M+): theoretical value 739.32, measured value 739.37.
Embodiment 11: the synthesis of compound 53:
The preparation method is the same as that of Example 1 for compound 5, the difference is that replacing raw material F1 with raw material F6.
Elemental analysis structure (molecular formula C57H41N): theoretical value C, 92.52；H,5.59；N,1.89；Test value: C,
92.53；H,5.61；N,1.92.ESI-MS(m/z)(M+): theoretical value 739.32, measured value 739.38.
Embodiment 12: the synthesis of compound 63:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol raw material E4,0.012mol raw material F5,150ml is added
Toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5mol Pd2(dba)3, 5 × 10-5Mol tri-tert-butylphosphine,
105 DEG C are heated to, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature,
Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity
98.9%, yield 66.7%；
Elemental analysis structure (molecular formula C57H41N): theoretical value C, 92.52；H,5.59；N,1.89；Test value: C,
92.55；H,5.61；N,1.85.ESI-MS(m/z)(M+): theoretical value 739.32, measured value 739.39.
Embodiment 13: the synthesis of compound 75:
The preparation method of compound 30 is with embodiment 7, the difference is that replacing raw material F4 with raw material F6.
Elemental analysis structure (molecular formula C57H41N): theoretical value C, 92.52；H,5.59；N,1.89；Test value: C,
92.55；H,5.61；N,1.85.ESI-MS(m/z)(M+): theoretical value 739.32, measured value 739.34.
Embodiment 14: the synthesis of compound 81:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate H1,0.024mol raw material D3 be added,
150ml toluene is stirred, then addition 0.04mol sodium carbonate, and 2 × 10-4molPd(PPh3)4, 105 DEG C are heated to, reflux is anti-
It answers 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate are depressurized
It rotates (- 0.09MPa, 85 DEG C), crosses neutral silica gel column, obtain target product, HPLC purity 99.2%, yield 73.5%；
Elemental analysis structure (molecular formula C60H37NO2): theoretical value C, 89.64；H,4.64；N,1.74；O,3.98；Test
Value: C, 89.66；H,4.61；N,1.72；O,4.01.ESI-MS(m/z)(M+): theoretical value 803.28, measured value are
803.34。
Embodiment 15: the synthesis of compound 91:
The preparation method of compound 30 is with embodiment 7, the difference is that replacing raw material F4 with raw material F8.
Elemental analysis structure (molecular formula C57H41N): theoretical value C, 92.52；H,5.59；N,1.89；Test value: C,
92.55；H,5.60；N,1.86.ESI-MS(m/z)(M+): theoretical value 739.32, measured value 739.34.
Embodiment 16: the synthesis of compound 99:
The preparation method is the same as that of Example 1 for compound 5, the difference is that replacing raw material F1 with raw material F9.
Elemental analysis structure (molecular formula C60H40N2): theoretical value C, 91.34；H,5.11；N,3.55；Test value: C,
91.31；H,5.12；N,3.57.ESI-MS(m/z)(M+): theoretical value 788.32, measured value 788.39.
Embodiment 17: the synthesis of compound 109:
The preparation method of compound 30 is with embodiment 7, the difference is that replacing raw material F4 with raw material F9.
Elemental analysis structure (molecular formula C60H40N2): theoretical value C, 91.34；H,5.11；N,3.55；Test value: C,
91.35；H,5.09；N,3.57.ESI-MS(m/z)(M+): theoretical value 788.32, measured value 788.41.
Embodiment 18: the synthesis of compound 146:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate H2,0.024mol raw material B10 be added,
150ml toluene is stirred, then addition 0.04mol sodium carbonate, and 2 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, reflux
Reaction 24 hours samples contact plate, and display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate are subtracted
Pressure revolving (- 0.09MPa, 85 DEG C) crosses neutral silica gel column, obtains target product, HPLC purity 99.2%, yield 73.5%；
Elemental analysis structure (molecular formula C54H33NO2): theoretical value C, 89.11；H,4.57；N,1.92；O,4.40；Test
Value: C, 89.14；H,4.55；N,1.93；O,4.38.ESI-MS(m/z)(M+): theoretical value 727.25, measured value are
727.33。
Embodiment 19: the synthesis of compound 158:
(1) in the there-necked flask of 250ml, lead under nitrogen protection, the bromo- 9H carbazole of 0.01mol 3- is added, 0.012mol is former
Expect that B10,150ml toluene are stirred, then addition 0.02mol sodium carbonate, 1 × 10-4mol Pd(PPh3)4, it is heated to 105
DEG C, back flow reaction 24 hours, contact plate is sampled, display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate
It carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel column, obtain target product, HPLC purity 99.2%, yield
75.5%；
(2) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate S1,0.012mol raw material F1 be added,
150ml toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5mol Pd2(dba)3, 5 × 10-5The tertiary fourth of mol tri-
Base phosphine is heated to 105 DEG C, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；It naturally cools to
Room temperature, filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity
99.3%, yield 55.7%；
Elemental analysis structure (molecular formula C48H29NO2): theoretical value C, 88.46；H,4.49；N,2.15；O,4.91；Test
Value: C, 88.47；H,4.50；N,2.16；O,4.87.ESI-MS(m/z)(M+): theoretical value 651.22, measured value are
651.31。
Embodiment 20: the synthesis of compound 159:
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol intermediate E 5,0.012mol raw material B10,
150ml toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5mol Pd2(dba)3, 5 × 10-5The tertiary fourth of mol tri-
Base phosphine is heated to 105 DEG C, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；It naturally cools to
Room temperature, filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity
99.3%, yield 60.7%；
Elemental analysis structure (molecular formula C54H33NO2): theoretical value C, 89.11；H,4.57；N,1.92；O,4.40；Test
Value: C, 89.14；H,4.55；N,1.93；O,4.38.ESI-MS(m/z)(M+): theoretical value 727.25, measured value are
727.33。
The compounds of this invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as luminescent layer
Subjective and Objective materials'use.To the chemical combination 1 of the above embodiment of the present invention preparation, 5,9,11,13,17,27,30,51,53,63,75,
81,91,99,109,146,158,159 test for carrying out hot property, HOMO energy level respectively, testing result is as shown in table 1.
Table 2
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2 × 10- 5The toluene solution of mol/L；By differential scanning calorimetry, (DSC, German Nai Chi company DSC204F1 show that difference is swept to glass transition temperature Tg
Retouch calorimeter) measurement, 10 DEG C/min of heating rate；Highest occupied molecular orbital HOMO energy level and minimum occupied molecular orbital LUMO
Energy level is tested by photoelectron emissions spectrometer (AC-2 type PESA), is tested as atmospheric environment.
By upper table data it is found that organic compound prepared by the present invention has high glass transition temperature, material can be improved
Film phase stability, further increases device service life；Material of the present invention and existing application material have similar HOMO energy
While grade, also there is high triplet (T1), luminescent layer energy loss can be stopped, is imitated to promote device and shine
Rate.Therefore, the organic material that the present invention contains carbazole can effectively improve device after the different function layer for being applied to OLED device
Luminous efficiency and service life.
Below by way of device embodiments 1~19 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device
Application effect in part.Device embodiments 2~19 of the present invention, the device compared with device embodiments 1 of device comparative example 1
Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept
Unanimously, except that the emitting layer material in 1~8 pair of device of device embodiments converts；9~19 pairs of devices of device embodiments
The hole transport of part/electronic blocking layer material converts, and the performance test results of each embodiment obtained device are as shown in table 3.
Device embodiments 1:
As shown in Figure 1, a kind of electroluminescent device, preparation step include:
A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively
Minute, then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 10nm,
This layer is as hole injection layer 3；
C) on hole injection layer 3, hole mobile material NPB is deposited by vacuum evaporation mode, with a thickness of 60nm, the layer
For hole transmission layer 4；
D) on hole transmission layer 4, electron-blocking materials TPAC is deposited by vacuum evaporation mode, it, should with a thickness of 20nm
Layer is electronic barrier layer 5；
E) luminescent layer 6 is deposited on electronic barrier layer 5, material of main part is 1 He of compound of preparation of the embodiment of the present invention
Compound GH, dopant material are Ir (ppy)3, compound 1, GH and Ir (ppy)3Three's mass ratio is 50:50:10, with a thickness of
40nm；
F) on luminescent layer 6, electron transport material TPBI is deposited by vacuum evaporation mode, with a thickness of 40nm, this layer
Organic material is used as hole barrier/electron transfer layer 7；
G) on hole barrier/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electricity
Sub- implanted layer 8；
H) on electron injecting layer 8, vacuum evaporation cathode Al (100nm), the layer is cathode reflection electrode layer 9；
After the production for completing electroluminescent device according to above-mentioned steps, the driving voltage of measurement device, current efficiency, knot
Fruit is shown in Table 3.The molecular structural formula of associated materials is as follows:
Device embodiments 2:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: the compound 5 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 88:12 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device embodiments 3:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: the compound 11 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 92:8 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device embodiments 4:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: compound 51, GH and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 70:30:10 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/
The detection data of electroluminescent device obtained by Al (thickness: 100nm) is shown in Table 3.
Device embodiments 5:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: compound 63, GH and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 60:40:10 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/
The detection data of electroluminescent device obtained by Al (thickness: 100nm) is shown in Table 3.
Device embodiments 6:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: compound 75, GH and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 40:60:10 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/
The detection data of electroluminescent device obtained by Al (thickness: 100nm) is shown in Table 3.
Device embodiments 7:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: compound 81, GH and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 30:70:10 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/
The detection data of electroluminescent device obtained by Al (thickness: 100nm) is shown in Table 3.
Device embodiments 8:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: compound 91, GH and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:8 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/
The detection data of electroluminescent device obtained by Al (thickness: 100nm) is shown in Table 3.
Device embodiments 9:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 9) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 10:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 13) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 11:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 17) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 12:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 27) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 13:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 30) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 14:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 53) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 15:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 99) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole
Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness:
100nm) detection data of gained electroluminescent device is shown in Table 3.
Device embodiments 16:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 109) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device embodiments 17:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 146) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device embodiments 18:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 158) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device embodiments 19:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5
Standby compound 159) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty
Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm) gained electroluminescent device detection data be shown in Table 3.
Device comparative example 1:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT-
CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6
(thickness: 40nm, material: CBP and Ir (ppy)3Constituted by weight 90:10 blending)/hole barrier/electron transfer layer 7 (thickness
Degree: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).Gained electroluminescent
The detection data of device is shown in Table 3.
Table 3
| Number | Current efficiency (cd/A) | Color | LT95 service life (Hr)@5000nits |
| Device embodiments 1 | 52.3 | Green light | 53.7 |
| Device embodiments 2 | 48.5 | Green light | 39.7 |
| Device embodiments 3 | 47.3 | Green light | 48.9 |
| Device embodiments 4 | 55.8 | Green light | 55.7 |
| Device embodiments 5 | 56.1 | Green light | 56.3 |
| Device embodiments 6 | 54.2 | Green light | 54.4 |
| Device embodiments 7 | 52.3 | Green light | 57.3 |
| Device embodiments 8 | 54.6 | Green light | 55.1 |
| Device embodiments 9 | 45.1 | Green light | 33.7 |
| Device embodiments 10 | 44.6 | Green light | 36.8 |
| Device embodiments 11 | 42.7 | Green light | 34.9 |
| Device embodiments 12 | 48.5 | Green light | 30.7 |
| Device embodiments 13 | 43.7 | Green light | 28.8 |
| Device embodiments 14 | 44.6 | Green light | 29.2 |
| Device embodiments 15 | 43.5 | Green light | 27.8 |
| Device embodiments 16 | 40.8 | Green light | 29.7 |
| Device embodiments 17 | 48.4 | Green light | 30.8 |
| Device embodiments 18 | 44.9 | Green light | 28.1 |
| Device embodiments 19 | 48.5 | Green light | 31.6 |
| Device comparative example 1 | 32.5 | Green light | 13.4 |
Organic compound prepared by the present invention can be applied to the production of OLED luminescent device it can be seen from the result of table 3, and
And compared with device comparative example 1, either efficiency or service life obtain larger change, especially device than known OLED material
Service life obtain biggish promotion.The OLED device of further material preparation of the present invention is able to maintain longevity at high temperature
Life, by device embodiments 1~19 and device comparative example 1 in 85 DEG C of progress high temperature driven life tests, acquired results such as 4 institute of table
Show.
Table 4
From the data of table 4 it is found that device embodiments 1~19 are the device architecture of material of the present invention and known materials collocation,
It is compared with device comparative example 1, under high temperature, OLED device provided by the invention has the driving service life well.
By further experimental study, OLED device prepared by material of the present invention work limitation rate at low temperature is found
It is more stable, device embodiments 1,4,17 and device comparative example 1 are subjected to efficiency test, acquired results in -10~80 DEG C of sections
As shown in table 5.
Table 5
From the data of table 5 it is found that device embodiments 1,4,17 are the device architecture of material of the present invention and known materials collocation,
It is compared with device comparative example 1, not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.
Further to test beneficial effect caused by the compounds of this invention, by device embodiments 1 of the present invention and device ratio
Compared with the electric leakage current test that device made by example 1 carries out backward voltage, shown in test data Fig. 3, from Fig. 3 it can be seen that using this
The device embodiments 1 of invention compound are compared with device made by device comparative example 1, leakage current very little, and current curve is stablized,
Therefore, after material of the present invention is applied to element manufacturing, there is long service life.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of using carbazole as the compound of core, which is characterized in that shown in the structure of the compound such as general formula (1):
Wherein, Ar1、Ar2、Ar3Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one or more
One of a heteroatomic substituted or unsubstituted 5~60 yuan of heteroarylidenes, the hetero atom are nitrogen, oxygen or sulphur, Ar1、Ar2、
Ar3It can be identical or different；
In general formula (1), R1、R2、R3Independently be expressed as structure shown in hydrogen atom or general formula (2), R1、R2、R3It can phase
It is same or different, and R1、R2、R3It is not simultaneously hydrogen atom；
Wherein, X1It is expressed as oxygen atom, sulphur atom, selenium atom, C1-10Alkylidene, the aryl of linear or branched alkyl group substitution replace
Alkylidene, one of the imido grpup that replaces of alkyl-substituted imido grpup or aryl.
2. according to claim 1 a kind of using carbazole as the compound of core, which is characterized in that in general formula (1), Ar1、
Ar2、Ar3Independently be expressed as one of singly-bound, phenylene, biphenylene, naphthylene or sub-pyridyl group.
3. according to claim 1 a kind of using carbazole as the compound of core, which is characterized in that the compound it is specific
Structural formula are as follows:
In any one.
4. a kind of using carbazole as the preparation method of the compound of core characterized by comprising
Reaction equation using preparation method 1 is as follows:
Specific preparation process the following steps are included:
1) raw material A and raw material B being added in toluene and is dissolved, wherein the toluene dosage is every gram of raw material A using 30~
The molar ratio of 50ml toluene, the raw material A and raw material B are 1:(1.0~1.5)；
2) Pd (PPh is added into the reaction system of step 1)3)4And sodium carbonate, wherein the Pd (PPh3)4With mole of raw material A
Than for (0.005~0.01): 1, the molar ratio of the sodium carbonate and raw material A is (1.5~3.0): 1, obtain mixed solution；
3) it under nitrogen protection, by mixed solution obtained in step 2) in 95~110 DEG C, reacts 10~24 hours, it is naturally cold
But to room temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate C；
4) intermediate C obtained in step 3) and raw material D is added in toluene and is dissolved, wherein the toluene dosage is every
Gram intermediate C uses 30-50ml toluene, and the molar ratio of the intermediate C and raw material D are 1:(1.0~1.5)；
5) Pd (PPh is added into the reaction system of step 4)3)4And sodium carbonate, wherein the Pd (PPh3)4With rubbing for intermediate C
You are than being (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate C are (1.5~3.0): and 1, obtain mixed solution；
6) it under nitrogen protection, by mixed solution obtained in step 5) in 95~110 DEG C, reacts 10~24 hours, it is naturally cold
But to room temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate E；
7) intermediate E and raw material F being added in toluene and is dissolved, wherein the toluene dosage is every gram of intermediate E using 30~
The molar ratio of 50ml toluene, the intermediate E and raw material F are 1:(1.0~1.5)；
8) Pd is added into the reaction system in step 7)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide；The Pd2(dba)3With
The molar ratio of intermediate E is (0.005~0.01): 1, the molar ratio of the tri-tert-butylphosphine and intermediate E be (0.005~
0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate E is (1.5~3.0): 1, obtain mixed liquor；
9) under the protection of inert gas, mixed solution obtained in step 8) is reacted under the conditions of 95~110 DEG C of temperature
10~for 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains target
Product 1；
Reaction equation using preparation method 2 is as follows:
Specific preparation process the following steps are included:
1) raw material G and raw material F is added in toluene and is dissolved, wherein the toluene dosage is that every gram of raw material G uses 30-50ml first
The molar ratio of benzene, the middle raw material G and raw material F are 1:(1.0~1.5)；
2) Pd is added into the reaction system in step 1)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide；The Pd2(dba)3With
The molar ratio of raw material G is (0.005~0.01): 1, the molar ratio of the tri-tert-butylphosphine and raw material G is (0.005~0.02):
1, the molar ratio of the sodium tert-butoxide and raw material G are (1.5~3.0): 1, obtain mixed solution；
3) under the protection of inert gas, mixed solution obtained in step 2) is reacted under the conditions of 95~110 DEG C of temperature
10~for 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains centre
Body H；
4) intermediate H obtained in step 3) and raw material B is added in toluene and is dissolved, wherein the toluene dosage is in every gram
Mesosome H uses 30-50ml toluene, and the molar ratio of the intermediate H and raw material B is 1:(1.0~1.5)；
5) Pd (PPh is added into step 4) reaction system3)4And sodium carbonate, wherein the Pd (PPh3)4With mole of intermediate H
Than for (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate H are (1.5~3.0): 1, obtain mixed solution；
6) it under nitrogen protection, by mixed solution obtained in step 5) in 95~110 DEG C, reacts 10~24 hours, it is naturally cold
But to room temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate compound I；
7) intermediate compound I that step 6) obtains is added in toluene with raw material D and is dissolved, wherein the toluene dosage is every gram of centre
Body I uses 30~50ml toluene, and the molar ratio of the intermediate compound I and raw material D are 1:(1.0~1.5)；
8) Pd (PPh is added into step 7) reaction system3)4And sodium carbonate, wherein the Pd (PPh3)4With mole of intermediate compound I
Than for (0.005~0.01): 1, the molar ratio of the sodium carbonate and intermediate compound I is (1.5~3.0): 1；
9) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, cooled to room temperature, and
Filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain target product 2.
5. it is a kind of it is a kind of as described in any one of claims 1 to 3 using carbazole be the compound of core in organic electroluminescence device
In application.
6. a kind of organic electroluminescence device, which is characterized in that it is any to contain claims 1 to 3 including at least one layer of functional layer
Item is described a kind of using carbazole as the compound of core.
7. a kind of organic electroluminescence device according to claim 6, which is characterized in that the functional layer is luminescent layer.
8. a kind of organic electroluminescence device according to claim 6, which is characterized in that the functional layer is hole transmission layer
With electronic barrier layer.
9. the element of a kind of illumination or display, which is characterized in that including the described in any item organic electroluminescences of such as claim 5~8
Luminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114409589A (en) * | 2022-01-19 | 2022-04-29 | 南京高光半导体材料有限公司 | Compound containing carbazole structure and organic electroluminescent device |
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