CN109912578A - A kind of compound of the structure containing spiro fluorene and its application on organic electroluminescence device - Google Patents
A kind of compound of the structure containing spiro fluorene and its application on organic electroluminescence device Download PDFInfo
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Abstract
The invention discloses a kind of compound of structure containing spiro fluorene and its applications on organic electroluminescence device, this compound is because containing spiro fluorene structure, with very strong rigidity, and after connecting carbazole derivates long branched chain structure so that the compound have the characteristics that it is intermolecular be not easy to crystallize, be not easy to assemble, good film forming；The compounds of this invention is because parent nucleus has bipolarity, and branch is electron donating group, and branched group electron donation is strong and weak different, and therefore, the HOMO energy level of material is different, can be used as the use of different function layer material；In addition, the compounds of this invention triplet with higher, can effectively stop energy loss and be conducive to energy transmission.Therefore, after the compounds of this invention is applied to OLED device as organic electroluminescent functional layer material, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of compound containing spiro fluorene structure and its organic
Application on electroluminescent device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can not only be used to
New display product is manufactured, can be also used for production novel illumination product, and be expected to substitute existing liquid crystal display and fluorescent lamp
Illumination, be widely used prospect.OLED luminescent device is a kind of sandwich structure, including electrode material film layer, with
And it is clipped in the organic functional material between Different electrodes film layer, various different function materials are overlapped mutually together depending on the application
Collectively constitute OLED luminescent device.As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through
Positive and negative charge in electric field action organic layer functional material film layer, positive and negative charge is further compound in luminescent layer, that is, generates
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. the extension of large scales application field, still, the application of the luminous efficiency of OLED device, the performances such as service life and product is wanted
It asks to compare and need further to be promoted.Research for improving OLED luminescent device performance specifically includes that the driving for reducing device
Voltage improves the luminous efficiency of device, improves the service life etc. of device.In order to realize that the continuous of performance of OLED device mentions
It rises, not only OLED device structure and manufacture craft are innovated, also oled light sulfate ferroelectric functional material is constantly studied
And innovation, to create the OLED functional material of higher performance.Applied to OLED device oled light sulfate ferroelectric functional material from
Two major classes, i.e. charge injection transmission material and luminescent material can be substantially divided on way, charge injection transmission material can divide again
Transmission material and hole barrier materials are injected for electron injection transmission material, electron-blocking materials, hole, and luminescent material packet
Include main body luminescent material and dopant material.High performance OLED luminescent device, it is desirable that various organic functional materials must have good
Good photoelectric characteristic, for example, as charge transport materials, it is desirable that there is good carrier mobility, higher vitrifying turns
Temperature etc., the material of main part of luminescent layer will have 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 architecture then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics biography
A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is infused including at least hole
Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form with rich and more
The characteristics of sample.In addition, used photoelectric functional material has relatively strong for the collocation of the OLED device of different structure
Selectivity, performance of the identical material in different structure device, it is also possible to completely it is totally different.Therefore, for current
The industry application requirement of OLED device and the different function film layer of OLED device, the photoelectric characteristic demand of device, it is necessary to select
It selects and is more suitable for, OLED functional material or combination of materials with high performance are just able to achieve the high efficiency of device, long-life and low
The overall characteristic of voltage.For current OLED shows the actual demand of Lighting Industry, the development of OLED material at present is also much
The requirement for lagging behind panel manufacturing enterprise, the organic functional material as material enterprise development higher performance are particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of structure containing spiro fluorene compound and its
Application on organic electroluminescence device.The compounds of this invention contains spiro fluorene structure, glass transition temperature with higher and
Molecule thermal stability, suitable HOMO and lumo energy after being applied to OLED device production, can effectively improve shining for device
The service life of efficiency and OLED device.
Technical scheme is as follows: a kind of compound of the structure containing spiro fluorene, the structure of the compound such as general formula (1) institute
Show:
Wherein, X is expressed as oxygen atom, C1-10Alkylidene, the alkane of alkylidene, aryl substitution that linear or branched alkyl group replaces
One of the imido grpup that the imido grpup or aryl that base replaces replace；
Z is expressed as N atom or C-H identical or differently；
M, n, p, q are equal to 0 or 1；And m+n+p+q >=1；
A, C, D, E are optionally by one or more R1Substituted carbazole derivates；A, C, D, E are same or different；
R1It is expressed as substituted or unsubstituted C6To C30Aryl and substituted or unsubstituted C5To C30One of heteroaryl；
The hetero atom is nitrogen, oxygen or sulphur.
On the basis of above scheme, the present invention can also do following improvement.
Preferably, the compound of a kind of structure containing spiro fluorene, described group A, C, D, E can be indicated with general formula (2)；
In general formula (2), R2It is expressed as substituted or unsubstituted C6-60Aryl replaces or not containing one or more hetero atoms
Substituted C6-60One of heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；
Ar is expressed as substituted or unsubstituted C6To C30Arlydene and substituted or unsubstituted C5To C30In heteroarylidene
It is a kind of；The hetero atom is nitrogen, oxygen or sulphur；
R3It is expressed as hydrogen atom, phenyl, naphthalene, xenyl, anthryl, furyl, carbazyl, naphthyridines base, quinolyl, thiophene
One of base, pyridyl group, base, 9,9- dimethyl fluorenyl, phenanthryl, dibenzofuran group, dibenzothiophene；
R3It is also denoted as general formula (3), general formula (4), structure shown in general formula (5) or general formula (6)；
In general formula (3) and general formula (4), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, nitrogen-atoms, C1-10Directly
The imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl of alkylidene, aryl substitution that chain or branched alkyl replace replace
One of；
General formula (3), general formula (4), general formula (5) pass through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key and general formula (2) and ring company
It connects；
In general formula (6), R4、R5Independently be expressed as substituted or unsubstituted C6-60Aryl, containing one or more miscellaneous
One of substituted or unsubstituted 5-60 unit's heteroaryl of atom；The hetero atom is nitrogen, oxygen or sulphur.
Preferably, the compound of a kind of structure containing spiro fluorene, appointing in general formula (1) the structure meeting formula (I) or formula (II)
It is a kind of:
Preferably, the compound of a kind of structure containing spiro fluorene, the structure meeting formula (III) of described group A, C, D, E, formula (IV),
Any one of formula (V) or formula (VI):
Preferably, the compound of a kind of structure containing spiro fluorene, the Ar are indicated are as follows: Or one of singly-bound；
Preferably, the compound of a kind of structure containing spiro fluorene, the R2It is expressed as phenyl, naphthalene, xenyl, anthryl, furans
Base, carbazyl, naphthyridines base, quinolyl, thienyl, pyridyl group, base, 9,9- dimethyl fluorenyl, phenanthryl, dibenzofuran group,
One of dibenzothiophene；
The R4、R5Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, dibenzo
One of thiophene, 9,9- dimethyl fluorene or N- phenyl carbazole.
Preferably, the compound of a kind of structure containing spiro fluorene, the concrete structure formula of the compound are as follows:
In
It is any.
The present invention also provides a kind of preparation method of the compound of structure containing spiro fluorene, the reactional equation that occurs in preparation process
Formula are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) with raw material A andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of raw material A uses 30-50ml toluene, the raw material A withMole
Than for 1:(1.0~1.5)；
2) Pd (PPh is added into reaction system 1)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of raw material A: 1, the sodium carbonate and raw material A
Molar ratio is (1.5~3.0): 1；
3) 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 intermediate N；
4) with intermediate N andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate N uses 30-50ml toluene, the intermediate N with's
Molar ratio is 1:(1.0~1.5)；
5) Pd (PPh is added into reaction system 4)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate N: 1, the sodium carbonate and intermediate
The molar ratio of body N is (1.5~3.0): 1；
6) 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 intermediate M；
7) with intermediate M andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate M uses 30-50ml toluene, the intermediate M with's
Molar ratio is 1:(1.0~1.5)；
8) Pd (PPh is added into reaction system 7)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate M: 1, the sodium carbonate and intermediate
The molar ratio of body M 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 intermediate P；
10) with intermediate P andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate P uses 30-50ml toluene, the intermediate P with's
Molar ratio is 1:(1.0~1.5)；
11) Pd (PPh is added into reaction system 10)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate P: 1, the sodium carbonate and intermediate
The molar ratio of body P is (1.5~3.0): 1；
12) 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 compound.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function
Layer contains the compound of the structure containing spiro fluorene.
Preferably, a kind of organic electroluminescence device, including hole transmission layer/electronic barrier layer, the hole transmission layer/
Electronic barrier layer contains the compound of the structure containing spiro fluorene.
Preferably, a kind of organic electroluminescence device, including luminescent layer, the luminescent layer contain the chemical combination of the structure containing spiro fluorene
Object.
The present invention also provides a kind of illumination or display elements, including the organic electroluminescence device.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function
Layer contains the compound of the above-mentioned structure containing spiro fluorene.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the organic electroluminescence device, including hole transmission layer/electronic barrier layer, the hole transport
Layer/electronic barrier layer contains the compound of the structure containing spiro fluorene as described above.
Further, the organic electroluminescence device, including luminescent layer, the luminescent layer contain as described above containing spiral shell
Fluorene structured compound.
The present invention also provides a kind of illumination or display elements, including organic electroluminescence device as described above.
The present invention is beneficial to be had the technical effect that
The compounds of this invention connects carbazole derivates long branched chain structure, since branched group is given using spiro fluorene structure as skeleton
Electronic capability is strong and weak different, adjust the HOMO energy level of compound entirety structure can freely, the shallow compound of HOMO energy level can be made
For hole transmission layer/electronic barrier layer materials'use；The material of HOMO energy level depth can be used as inclined electron type luminescent layer material of main part
It uses.
In addition, spiro fluorene structure is bipolarity group, branch is backbone, destroys the symmetry of molecular structure, avoids
Intermolecular aggtegation；It using spiro fluorene structure as parent nucleus, avoids group and rotates freely, enhance center parent nucleus group
Rigidity, the branched group of the compounds of this invention also has very strong rigidity, therefore, molecule be not easy accumulative crystallization, have it is good at
Film property, and glass transition temperature with higher and thermal stability, so, when the compounds of this invention is applied to OLED device,
Membranous layer stability after can keeping material filming improves OLED device service life.
In addition, the compounds of this invention has high triplet, it can effectively stop energy loss and be conducive to energy to pass
It passs.Therefore, after compound of the present invention is applied to OLED device as organic electroluminescent functional layer material, the electricity of device
Efficiency is flowed, power efficiency and external quantum efficiency are greatly improved；Meanwhile clearly for device lifetime promotion, exist
There is good application effect in OLED luminescent device, there is 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；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 hinder for electronics
Barrier, 6 be luminescent layer, and 7 be hole barrier/electron transfer layer, and 8 be electron injecting layer, and 9 be cathode reflection electrode layer；
Fig. 2 is the efficiency curve diagram that device measures at different temperatures.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is specifically described.
Intermediate B can be synthesized by following the equation, by taking the synthesis of intermediate B 1 as an example:
(1) raw material 0.05mol B1 and 0.06mol raw material C is weighed, the toluene ethyl alcohol for being 1.5:1 with 100ml volume ratio is mixed
Bonding solvent dissolution；Add 50ml Na2CO3Aqueous solution, 0.0005mol Pd (PPh3)4；It under nitrogen protection, will be above-mentioned mixed
Solution to be closed at 95 DEG C, is stirred to react 4 hours, then cools to room temperature, filtering reacting solution, filtrate revolving crosses silicagel column,
Obtain intermediate S1；
(2) under nitrogen protection, 0.05mol intermediate S1 is weighed, with tetrahydrofuran stirring and dissolving；By mixed solution ice
Salt bath is cooled to 0 DEG C, and the tetrahydrofuran solution of the correspondence grignard reagent of 0.2mol brand-new is slowly added dropwise, and reacts at room temperature 12 hours,
Contact plate is sampled, display is remaining without intermediate S1, fully reacting；Naturally it places to room temperature, filtering, filtrate carries out vacuum rotary steam extremely
Without fraction, neutral silica gel column is crossed, intermediate M1 is obtained；
(3) under nitrogen protection, intermediate 0.04mol M1 is weighed, the dense H for being 1:2.0 with 100ml volume ratio3PO4With water
Mixed liquor as solvent, dissolution reacts at room temperature 12 hours, samples contact plate, display is remaining without intermediate M1, fully reacting；Add
Enter NaOH aqueous solution and be neutralized to pH=7, methylene chloride extraction is added, layering takes organic phase to filter, filtrate decompression is rotated to nothing
Fraction crosses neutral silica gel column, obtains intermediate N1；
(4) in the there-necked flask of 250ml, lead under nitrogen protection, sequentially add 0.04mol intermediate N1,0.05mol connection boron
Sour pinacol ester, 0.06mol acetic acid, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitrae-dioxane, be stirred, heat
It to 80 DEG C, reacts 24 hours, samples contact plate, display is remaining without intermediate N1, fully reacting；Cooled to room temperature, after adding water
There is solid precipitation, filter, filter cake is taken to be dried with vacuum oven, then cross neutral silica gel column, obtain boric acid ester compound, uses
Tetrahydrofuran dissolution, is added 0.05mol sodium metaperiodate, adjusts pH to 2 with HCL aqueous solution, hydrolysis 12 hours is stirred at room temperature, takes
Sampling point plate, display completely, are diluted with water reaction solution, are extracted with ethyl acetate, be layered, take without boric acid ester compound residue, hydrolysis
Organic phase is evaporated under reduced pressure to no fraction, is then washed with n-hexane, and intermediate B 1 is obtained；HPLC purity 99.2%, yield
65.9%；
Elemental analysis structure (molecular formula C27H22BNO2): theoretical value C, 80.41；H,5.50；N,2.68；B,3.47；O,
7.93；Test value: C, 80.43；H,5.52；N,2.69；B,3.49；O,7.95.
HPLC-MS (m/z): theoretical value 403.17, measured value 403.19.
By taking the synthesis of intermediate B 6 as an example:
(1) in the there-necked flask of 250ml, raw material 0.05mol B3,100ml acetic acid is added, stirring and dissolving is dropped with ice salt bath
Temperature is to 0 DEG C；Weigh 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system,
It after completion of dropwise addition, is warmed to room temperature, is stirred to react 12 hours；Contact plate is sampled, display is remaining without raw material B3, fully reacting；Add NaOH
Aqueous solution neutralization reaction liquid, is extracted with dichloromethane, and layering takes organic phase to filter, and filtrate decompression is rotated to no fraction, excessively in
Property silicagel column, obtains intermediate O, HPLC purity 99.3%, yield 68.9%；
(2) in the there-necked flask of 250ml, lead under nitrogen protection, addition 0.05mol intermediate O, 0.06mol phenyl boric acid,
100ml toluene, is stirred, and adds 0.0005mol Pd (PPh3)4, 0.075mol potassium carbonate, 50ml water and ethyl alcohol volume
Mixed liquor than 1:1, stirring are warming up to 120 DEG C, back flow reaction 24 hours, sample contact plate, display is remaining without intermediate O, reaction
Completely；Cooled to room temperature, filtering, filtrate layered take organic phase vacuum rotary steam to no fraction, cross neutral silica gel column, obtain
Intermediate S3, HPLC purity 99.3%, yield 68.2%；
(3) in the there-necked flask of 250ml, lead under nitrogen protection, 0.04mol intermediate S3,0.05mol triphenyl is added
Phosphine, 100ml o-dichlorohenzene, are stirred, and are heated to 180 DEG C, react 12 hours, sample contact plate, and display is surplus without intermediate S3
It is remaining, fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate
M3, HPLC purity 99.2%, yield 75.5%；
(4) in the there-necked flask of 250ml, lead under nitrogen protection, 0.03mol intermediate M3, bromobenzene, 150ml toluene be added,
It is stirred, adds 0.09mol sodium tert-butoxide, 0.002molPd2(dba)3, 0.002mol tri-tert-butylphosphine, be heated with stirring to
115 DEG C, back flow reaction 24 hours, contact plate is sampled, display is remaining without intermediate M3, fully reacting；Cooled to room temperature, mistake
Filter, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate N6, HPLC purity 99.1%, yield 65.9%；
(5) in the there-necked flask of 250ml, lead under nitrogen protection, sequentially add 0.04mol intermediate N6,0.05mol connection boron
Sour pinacol ester, 0.06mol acetic acid, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitrae-dioxane, be stirred, heat
It to 80 DEG C, reacts 24 hours, samples contact plate, display is remaining without intermediate N6, fully reacting；Cooled to room temperature, after adding water
There is solid precipitation, filter, filter cake is taken to be dried with vacuum oven, then cross neutral silica gel column, obtain boric acid ester compound, uses
Tetrahydrofuran dissolution, is added 0.05mol sodium metaperiodate, adjusts pH to 2 with HCL aqueous solution, hydrolysis 12 hours is stirred at room temperature, takes
Sampling point plate, display completely, are diluted with water reaction solution, are extracted with ethyl acetate, be layered, take without boric acid ester compound residue, hydrolysis
Organic phase is evaporated under reduced pressure to no fraction, is then washed with n-hexane, and intermediate B 6 is obtained；HPLC purity 99.2%, yield
65.9%；
Elemental analysis structure (molecular formula C30H21BN2O2): theoretical value C, 79.66；H,4.68；N,6.19；B,2.39；O,
7.07；Test value: C, 79.69；H,4.58；N,6.24；B,2.439；O,7.13.
HPLC-MS (m/z): theoretical value 452.17, measured value 452.29.
Raw material B, intermediate S, intermediate M, intermediate N and intermediate B, specific structure are as shown in table 1；
Table 1
Embodiment 1: the synthesis of compound 2:
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol raw material A 1,0.012mol intermediate B 3,
150ml toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5molPd2(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 remaining without raw material A 1, fully reacting；Natural cooling
To room temperature, filtering, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel column, obtains target product, HPLC is pure
Degree 99.3%, yield 84.7%；
Elemental analysis structure (molecular formula C49H29NO2): theoretical value C, 88.67；H,4.40；N,2.11；O,4.82；Test
Value: C, 88.75；H,4.45；N,2.15；O,4.86.ESI-MS(m/z)(M+): theoretical value 663.22, measured value are
663.29。
Embodiment 2: the synthesis of compound 7:
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol raw material A 1,0.012mol intermediate B 2,
150ml toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5molPd2(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 remaining without raw material A 1, fully reacting；Natural cooling
To room temperature, filtering, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel column, obtains target product, HPLC is pure
Degree 99.5%, yield 82.9%；
Elemental analysis structure (molecular formula C52H35NO): theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test
Value: C, 90.58； H,5.13；N,2.06；O,2.35.ESI-MS(m/z)(M+): theoretical value 689.27, measured value are
689.32。
Embodiment 3: the synthesis of compound 16:
The preparation method is the same as that of Example 1 for compound 16, the difference is that replacing intermediate B 3 with intermediate B 1.Element point
Analyse structure (molecular formula C52H35NO): theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test value: C, 90.57；H,
5.16；N, 2.09；O,2.37.ESI-MS(m/z)(M+): theoretical value 689.27, measured value 689.36.
Embodiment 4: the synthesis of compound 22:
The preparation method is the same as that of Example 1 for compound 22, the difference is that replacing intermediate B 3 with intermediate B 13.Element
Analyze structure (molecular formula C47H29NO): theoretical value C, 90.50；H,4.69；N,2.25；O,2.56；Test value: C, 90.57；H,
4.73；N, 2.29；O,2.58.ESI-MS(m/z)(M+): theoretical value 623.22, measured value 623.28.
Embodiment 5: the synthesis of compound 45:
The preparation method is the same as that of Example 1 for compound 45, the difference is that replacing raw material A 1 with raw material A 2.Elemental analysis knot
Structure (molecular formula C49H29NO2): theoretical value C, 88.67；H,4.40；N,2.11；O,4.82；Test value: C, 88.73；H,4.49；
N,2.16；O, 4.87.ESI-MS(m/z)(M+): theoretical value 663.22, measured value 663.31.
Embodiment 6: the synthesis of compound 50:
The preparation method is the same as that of Example 1 for compound 50, the difference is that raw material A 1 is replaced with raw material A 2, with intermediate B 2
Replace intermediate B 3.Elemental analysis structure (molecular formula C52H35NO): theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；
Test value: C, 90.59；H,5.18；N,2.07；O,2.36.ESI-MS(m/z)(M+): theoretical value 689.27, measured value are
689.33。
Embodiment 7: the synthesis of compound 55:
The preparation method is the same as that of Example 1 for compound 55, the difference is that raw material A 1 is replaced with raw material A 2, with intermediate B 5
Replace intermediate B 3.Elemental analysis structure (molecular formula C55H34N2O): theoretical value C, 89.41；H,4.64；N,3.79；O,2.17；
Test value: C, 89.49；H,4.68；N,3.83；O,2.22.ESI-MS(m/z)(M+): theoretical value 738.27, measured value are
738.33。
Embodiment 8: the synthesis of compound 62:
The preparation method is the same as that of Example 1 for compound 62, the difference is that raw material A 1 is replaced with raw material A 2, with intermediate B 9
Replace intermediate B 3.Elemental analysis structure (molecular formula C49H29NOS): theoretical value C, 86.57；H,4.30；N,2.06；O,
2.35；S,4.72；Test value: C, 86.59；H,4.38；N,2.13；O,2.42；S,4.77.ESI-MS(m/z)(M+): it is theoretical
Value is 679.20, measured value 679.28.
Embodiment 9: the synthesis of compound 68:
The preparation method is the same as that of Example 1 for compound 68, the difference is that replacing raw material A 1 with raw material A 2, uses intermediate
B12 replaces intermediate B 3.Elemental analysis structure (molecular formula C55H36N2O): theoretical value C, 89.16；H,4.90；N,3.78；O,
2.16；Test value: C, 89.19；H,4.98；N,3.83；O,2.25.ESI-MS(m/z)(M+): theoretical value 740.28, actual measurement
Value is 740.35.
Embodiment 10: the synthesis of compound 88:
The preparation method is the same as that of Example 1 for compound 88, the difference is that raw material A 1 is replaced with raw material A 3, with intermediate B 6
Replace intermediate B 3.Elemental analysis structure (molecular formula C53H32N4O): theoretical value C, 85.92；H,4.35；N,7.56；O,2.16；
Test value: C, 85.97；H,4.38；N,7.61；O,2.23.ESI-MS(m/z)(M+): theoretical value 740.26, measured value are
740.35。
Embodiment 11: the synthesis of compound 106:
The preparation method is the same as that of Example 1 for compound 106, the difference is that replacing raw material A 1 with raw material A 4, uses intermediate
B4 replaces intermediate B 3.Elemental analysis structure (molecular formula C52H35NO): theoretical value C, 90.54；H,5.11；N,2.03；O,
2.32；Test value: C, 90.61；H,5.17；N,2.05；O,2.38.ESI-MS(m/z)(M+): theoretical value 689.27, actual measurement
Value is 689.35.
Embodiment 12: the synthesis of compound 121:
The preparation method is the same as that of Example 1 for compound 121, the difference is that replacing raw material A 1 with raw material A 5, uses intermediate
B13 replaces intermediate B 3.Elemental analysis structure (molecular formula C47H29NO): theoretical value C, 90.50；H,4.69；N,2.25；O,
2.56；Test value: C, 90.56；H,4.75N,2.32；O,2.59.ESI-MS(m/z)(M+): theoretical value 623.22, actual measurement
Value is 623.31.
Embodiment 13: the synthesis of compound 123:
The preparation method is the same as that of Example 1 for compound 123, the difference is that replacing raw material A 1 with raw material A 5, uses intermediate
B11 replaces intermediate B 3.Elemental analysis structure (molecular formula C55H36N2O): theoretical value C, 89.16；H,4.90；N,3.78；O,
2.16；Test value: C, 89.23；H,4.97；N,3.82；O,2.23.ESI-MS(m/z)(M+): theoretical value 740.28, actual measurement
Value is 740.37.
Embodiment 14: the synthesis of compound 129:
The preparation method is the same as that of Example 1 for compound 129, the difference is that replacing raw material A 1 with raw material A 5, uses intermediate
B12 replaces intermediate B 3.Elemental analysis structure (molecular formula C55H36N2O): theoretical value C, 89.16；H,4.90；N,3.78；O,
2.16；Test value: C, 89.21；H,4.95；N,3.85；O,2.21.ESI-MS(m/z)(M+): theoretical value 740.28, actual measurement
Value is 740.33.
Embodiment 15: the synthesis of compound 137:
The preparation method is the same as that of Example 1 for compound 137, the difference is that replacing raw material A 1 with raw material A 6, uses intermediate
B5 replaces intermediate B 3.Elemental analysis structure (molecular formula C54H33N3O): theoretical value C, 87.66；H,4.50；N,5.68；O,
2.16；Test value: C, 87.71；H,4.58；N,5.73；O,2.25.ESI-MS(m/z)(M+): theoretical value 739.26, actual measurement
Value is 739.32.
Embodiment 16: the synthesis of compound 153:
The preparation method is the same as that of Example 1 for compound 153, the difference is that replacing raw material A 1 with raw material A 7, uses intermediate
B8 replaces intermediate B 3.Elemental analysis structure (molecular formula C49H29NO2): theoretical value C, 88.67；H,4.40；N,2.11；O,
4.82；Test value: C, 88.71；H,4.45；N,2.176；O,4.86.ESI-MS(m/z)(M+): theoretical value 663.22, it is real
Measured value is 663.32.
Embodiment 17: the synthesis of compound 154:
The preparation method is the same as that of Example 1 for compound 154, the difference is that replacing raw material A 1 with raw material A 7, uses intermediate
B6 replaces intermediate B 3.Elemental analysis structure (molecular formula C55H34N2O): theoretical value C, 89.41；H,4.64；N,3.79；O,
2.17；Test value: C, 89.47；H,4.68；N,3.83；O,2.23.ESI-MS (m/z) (M+): theoretical value 738.27, actual measurement
Value is 738.32.
Embodiment 18: the synthesis of compound 167:
The preparation method is the same as that of Example 1 for compound 167, the difference is that replacing raw material A 1 with raw material A 2, uses intermediate
B10 replaces intermediate B 3.Elemental analysis structure (molecular formula C47H29NO): theoretical value C, 90.50；H,4.69；N,2.25；O,
2.56；Test value: C, 90.58；H,4.73 N,2.29；O,2.61.ESI-MS (m/z) (M+): theoretical value 623.22, actual measurement
Value is 623.33.
Embodiment 19: the synthesis of compound 183:
The preparation method is the same as that of Example 1 for compound 183, the difference is that raw material A 1 is replaced with raw material A 8, with raw material B2
Replace raw material B3.Elemental analysis structure (molecular formula C55H41N): theoretical value C, 92.27；H,5.77；N,1.96；Test value: C,
92.32； H,5.81；N,2.03.ESI-MS(m/z)(M+): theoretical value 715.32, measured value 715.37.
Embodiment 20: the synthesis of compound 195:
The preparation method is the same as that of Example 1 for compound 195, the difference is that replacing raw material A 1 with raw material A 9, uses intermediate
B9 replaces intermediate B 3.Elemental analysis structure (molecular formula C52H35NS): theoretical value C, 88.48；H,5.00；N,1.98；S,
4.54；Test value: C, 88.53；H,5.07；N,2.03；S,4.57.ESI-MS(m/z)(M+): theoretical value 705.25, actual measurement
Value is 705.31.
Embodiment 21: the synthesis of compound 200:
The preparation method is the same as that of Example 1 for compound 200, the difference is that replacing raw material A 1 with raw material A 10, uses intermediate
B11 replaces intermediate B 3.Elemental analysis structure (molecular formula C58H42N2): theoretical value C, 90.83；H,5.52；N,3.65；Test
Value: C, 90.87；H,5.55；N,3.67.ESI-MS(m/z)(M+): theoretical value 766.33, measured value 766.39.
This organic compound uses in luminescent device, has high glass transition temperature (Tg) and triplet
(T1), suitable HOMO, lumo energy act not only as hole transmission layer/electronic barrier layer materials'use, are alternatively arranged as
Emitting layer material uses.Hot property, T1 energy level and HOMO energy level is carried out respectively to the compounds of this invention and current material to survey
Examination, the results are shown in Table 2.
Table 2
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10-5's
Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry
Instrument) measurement, 10 DEG C/min of heating rate；Highest occupied molecular orbital HOMO energy level is by photoelectron emissions spectrometer (AC-2 type
PESA it) tests, tests as atmospheric environment.
By upper table data it is found that NPB, CBP and TPAC material that comparison is applied at present, organic compound of the invention have
High glass transition temperature can be improved the phase stability of membrane material, further increase device service life；Material of the present invention
While material and application material have similar HOMO energy level, also there is high triplet (T1), luminescent layer can be stopped
Energy loss, to promote device light emitting efficiency.Therefore, the organic material that the present invention contains spiro fluorene structure is being applied to OLED
After the different function layer of device, the luminous efficiency and service life of device can be effectively improved.
Below by way of device embodiments 1~21 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 2~21 of the present invention, the device compared with device embodiments 1 of device comparative example 1
The manufacture craft of part is identical, and uses identical baseplate material and electrode material, and the film thickness of electrode material is also protected
It holds unanimously, except that the emitting layer material in 1~12 pair of device of device embodiments converts；Device embodiments 12~
The hole transmission layer of 21 pairs of devices/electronic blocking layer material converts, and the performance test results of each embodiment obtained device are such 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 2 He of compound of preparation of the embodiment of the present invention
Compound GHN, dopant material are Ir (ppy)3, compound 2, GHN and Ir (ppy)3Three's mass ratio is 50:50:10, thickness
For 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 shown in 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 is (thick
Degree: 40nm, material: the compound 7 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 88:12 blending)/hole
Blocking/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm).
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 is (thick
Degree: 40nm, material: the compound 22 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 92:8 blending)/hole
Blocking/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick
Degree: 100nm).
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 is (thick
Degree: 40nm, material: compound 55, GHN 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: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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 is (thick
Degree: 40nm, material: compound 62, GHN 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: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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 is (thick
Degree: 40nm, material: compound 68, GHN 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: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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 is (thick
Degree: 40nm, material: compound 106, GHN 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: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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 is (thick
Degree: 40nm, material: compound 121, GHN 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: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 is (thick
Degree: 40nm, material: compound 137, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:12 blending structure
At)/hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer
6 (thickness: 40nm, material: compound 153, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3It is mixed by weight 50:50:10
Mix composition)/hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer
6 (thickness: 40nm, material: compound 195, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3It is mixed by weight 50:50:10
Mix composition)/hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer
6 (thickness: 40nm, material: compound 200, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3It is mixed by weight 50:50:10
Mix composition)/hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material:
LiF)/Al (thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 16 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 45 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 50 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 88 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 123 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 129 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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: the embodiment of the present invention of/electronic barrier layer 5
The compound 154 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
Device embodiments 20: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: the embodiment of the present invention of/electronic barrier layer 5
The compound 167 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
Device embodiments 21: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: the embodiment of the present invention of/electronic barrier layer 5
The compound 183 of preparation) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/
Hole barrier/electron transfer layer 7 (thickness: 40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al
(thickness: 100nm).
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 is (thick
Degree: 40nm, material: CBP and Ir (ppy)3Constituted by weight 90:10 blending)/hole barrier/electron transfer layer 7 (thickness:
40nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).Gained electroluminescent cell
The detection data of part is shown in Table 3.
Table 3
Organic compound of the present invention can be applied to the production of OLED luminescent device it can be seen from the result of table 3, and with than
It is compared compared with example, either efficiency or service life obtain larger change, the especially service life of device than known OLED material
Obtain biggish promotion.
Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality
Example 2,9,15 and device comparative example 1 are applied in -10~80 DEG C of progress efficiency tests, acquired results are as shown in table 4, Fig. 2.
Table 4
From the data of table 4 it is found that device embodiments 2,9,15 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.
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 (12)
1. a kind of compound of structure containing spiro fluorene, which is characterized in that shown in the structure of the compound such as general formula (1):
Wherein, X is expressed as oxygen atom, C1-10Alkylidene, the alkyl of alkylidene, aryl substitution that linear or branched alkyl group replaces take
One of the imido grpup that the imido grpup or aryl in generation replace；
Z is expressed as N atom or C-H identical or differently；
M, n, p, q are equal to 0 or 1；And m+n+p+q >=1；
A, C, D, E are optionally by one or more R1Substituted carbazole derivates；A, C, D, E are same or different；
R1It is expressed as substituted or unsubstituted C6To C30Aryl and substituted or unsubstituted C5To C30One of heteroaryl；It is described
Hetero atom is nitrogen, oxygen or sulphur.
2. a kind of compound of structure containing spiro fluorene according to claim 1, which is characterized in that described group A, C, D, E can
It is indicated with general formula (2)；
In general formula (2), R2It is expressed as substituted or unsubstituted C6-60It is aryl, substituted or unsubstituted containing one or more hetero atoms
C6-60One of heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；
Ar is expressed as substituted or unsubstituted C6To C30Arlydene and substituted or unsubstituted C5To C30One of heteroarylidene；
The hetero atom is nitrogen, oxygen or sulphur；
R3It is expressed as hydrogen atom, phenyl, naphthalene, xenyl, anthryl, furyl, carbazyl, naphthyridines base, quinolyl, thienyl, pyrrole
One of piperidinyl, base, 9,9- dimethyl fluorenyl, phenanthryl, dibenzofuran group, dibenzothiophene；
R3It is also denoted as general formula (3), general formula (4), structure shown in general formula (5) or general formula (6)；
In general formula (3) and general formula (4), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, nitrogen-atoms, C1-10Straight chain or
In the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl of alkylidene, aryl substitution that branched alkyl replaces replace
It is a kind of；
General formula (3), general formula (4), general formula (5) pass through CL1-CL2Key, CL2-CL3Key or CL3-CL4Key is connected with general formula (2) and ring；
In general formula (6), R4、R5Independently be expressed as substituted or unsubstituted C6-60Aryl contains one or more hetero atoms
One of substituted or unsubstituted 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
3. a kind of compound of structure containing spiro fluorene according to claim 1, which is characterized in that general formula (1) constructor
Any one of box-like (I) or formula (II):
4. a kind of compound of structure containing spiro fluorene according to claim 2, which is characterized in that described group A, C, D, E's
Any one of structure meeting formula (III), formula (IV), formula (V) or formula (VI):
5. a kind of compound of structure containing spiro fluorene according to claim 1, which is characterized in that the Ar is indicated are as follows:
Or one of singly-bound.
6. a kind of compound of structure containing spiro fluorene according to claim 2, which is characterized in that the R2It is expressed as phenyl, naphthalene
Base, xenyl, anthryl, furyl, carbazyl, naphthyridines base, quinolyl, thienyl, pyridyl group, base, 9,9- dimethyl fluorenyl,
One of phenanthryl, dibenzofuran group, dibenzothiophene；
The R4、R5Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, dibenzo thiophene
One of pheno, 9,9- dimethyl fluorene or N- phenyl carbazole.
7. compound according to claim 1, which is characterized in that the concrete structure formula of the compound are as follows:
In
It is any.
8. a kind of such as a kind of described in any item preparation methods of the compound of the structure containing spiro fluorene of claim 1-7, feature exist
In the reaction equation occurred in preparation process are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) with raw material A andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of raw material A uses 30-50ml toluene, the raw material A withMolar ratio be
1:(1.0~1.5)；
2) Pd (PPh is added into reaction system 1)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with raw material A is (0.005~0.01): 1, mole of the sodium carbonate and raw material A
Than for (1.5~3.0): 1；
3) 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 intermediate N；
4) with intermediate N andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate N uses 30-50ml toluene, the intermediate N withMole
Than for 1:(1.0~1.5)；
5) Pd (PPh is added into reaction system 4)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate N is (0.005~0.01): 1, the sodium carbonate is with intermediate N's
Molar ratio is (1.5~3.0): 1；
6) 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 intermediate M；
7) with intermediate M andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate M uses 30-50ml toluene, the intermediate M withMole
Than for 1:(1.0~1.5)；
8) Pd (PPh is added into reaction system 7)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate M is (0.005~0.01): 1, the sodium carbonate is with intermediate M's
Molar ratio 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 intermediate P；
10) with intermediate P andFor raw material, dissolved with toluene；
Wherein, the toluene dosage is that every gram of intermediate P uses 30-50ml toluene, the intermediate P withMole
Than for 1:(1.0~1.5)；
11) Pd (PPh is added into reaction system 10)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate P is (0.005~0.01): 1, the sodium carbonate is with intermediate P's
Molar ratio is (1.5~3.0): 1；
12) 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 compound.
9. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer
Compound containing the described in any item structures containing spiro fluorene of claim 1-7.
10. a kind of organic electroluminescence device according to claim 9, including hole transmission layer/electronic barrier layer, special
Sign is that the hole transmission layer/electronic barrier layer contains the chemical combination of the described in any item structures containing spiro fluorene of claim 1-7
Object.
11. a kind of organic electroluminescence device according to claim 9, including luminescent layer, which is characterized in that described to shine
Compound of the layer containing the described in any item structures containing spiro fluorene of claim 1-7.
12. a kind of illumination or display element, which is characterized in that including the described in any item organic electroluminescence hairs of such as claim 9-11
Optical device.
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| CN110759939A (en) * | 2018-07-25 | 2020-02-07 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
| CN110818726A (en) * | 2019-10-25 | 2020-02-21 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method thereof and electroluminescent device |
| CN111518109A (en) * | 2019-02-01 | 2020-08-11 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
| CN112876465A (en) * | 2019-11-29 | 2021-06-01 | 上海和辉光电有限公司 | Oxadiazole-substituted organic light-emitting material and OLED device |
| WO2021177634A3 (en) * | 2020-03-02 | 2021-10-28 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same and electronic device thereof |
| JP2021530518A (en) * | 2019-01-30 | 2021-11-11 | ソリュース先端素材株式会社Solus Advanced Materials Co., Ltd. | Organic luminescent compounds and organic electroluminescent devices using them |
| WO2022120945A1 (en) * | 2020-12-08 | 2022-06-16 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method therefor and electroluminescent device |
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| CN110759939A (en) * | 2018-07-25 | 2020-02-07 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
| CN110759939B (en) * | 2018-07-25 | 2023-06-16 | 北京绿人科技有限责任公司 | Organic compound, application thereof and organic electroluminescent device |
| JP2021530518A (en) * | 2019-01-30 | 2021-11-11 | ソリュース先端素材株式会社Solus Advanced Materials Co., Ltd. | Organic luminescent compounds and organic electroluminescent devices using them |
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| CN110818726A (en) * | 2019-10-25 | 2020-02-21 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method thereof and electroluminescent device |
| CN112876465A (en) * | 2019-11-29 | 2021-06-01 | 上海和辉光电有限公司 | Oxadiazole-substituted organic light-emitting material and OLED device |
| CN112876465B (en) * | 2019-11-29 | 2023-07-04 | 上海和辉光电股份有限公司 | Oxadiazole-substituted organic luminescent material and OLED device |
| WO2021177634A3 (en) * | 2020-03-02 | 2021-10-28 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using same and electronic device thereof |
| WO2022120945A1 (en) * | 2020-12-08 | 2022-06-16 | 武汉华星光电半导体显示技术有限公司 | Hole transport material, preparation method therefor and electroluminescent device |
| WO2022173203A1 (en) * | 2021-02-09 | 2022-08-18 | 주식회사 엘지화학 | Compound and organic electronic device comprising same |
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