CN110511234B - Novel heterocyclic spiro-structure compound and application thereof in OLED (organic light emitting diode) device - Google Patents

Novel heterocyclic spiro-structure compound and application thereof in OLED (organic light emitting diode) device Download PDF

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CN110511234B
CN110511234B CN201910867187.8A CN201910867187A CN110511234B CN 110511234 B CN110511234 B CN 110511234B CN 201910867187 A CN201910867187 A CN 201910867187A CN 110511234 B CN110511234 B CN 110511234B
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CN110511234A (en
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范洪涛
呼建军
梁现丽
段陆萌
黄春雪
杭德余
李仲庆
曹占广
刘阳
班全志
李继响
罗忠林
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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Abstract

The invention relates to a novel heterocyclic spiro-structure compound, which has a structure shown as a general formula I; in the general formula I, E1、E2Each independently represents O, S or a Se atom, and the two are different; r1、R2、R3、R4Each independently represents an aromatic group having electron donating properties or being neutral, containing n benzene rings and/or aromatic heterocyclic rings, or represents an H atom; and n represents an integer of 1-7. The compound provided by the invention takes a spiro structure as a main body, the main body structure has a rigid structure and an electron-rich structural unit, excellent hole transport performance can be provided, and good thermal stability is achieved. An electron-donating group or a neutral group is introduced into the structure, so that the organic light-emitting diode can be well applied to OLED devices and used as a hole transport material.

Description

Novel heterocyclic spiro-structure compound and application thereof in OLED (organic light emitting diode) device
Technical Field
The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a novel organic material with a heterocyclic spiro structure and application thereof.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
The organic hole transport material reported at present has the defects that the molecular weight is generally small, the glass transition temperature of the material is low, the material is easy to crystallize after repeated charging and discharging in the use process of the material, and the uniformity of a thin film is damaged, so that the service life of the material is influenced. Therefore, the stable and efficient organic hole transport material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the organic hole transport material has important practical application value.
Disclosure of Invention
The invention aims to provide a novel OLED material with low driving voltage and high luminous efficiency for a device and application of the organic material in an OLED device.
In order to develop a compound with the properties, a novel spiro-structure compound is designed, a mother core of the series of compounds has a rigid structure and an electron-rich structural unit, the series of compounds can provide excellent hole transport property, have good thermal stability and can be well applied to OLED devices, the compound is represented by a general formula I, and the compound can be applied to OLED devices to achieve the purpose. Namely, the invention provides a novel heterocyclic spiro-structure compound, which has a structure shown as a general formula I:
Figure BDA0002201602140000011
in the general formula I, E1、E2Each independently represents O, S or a Se atom, and the two are different; r1、R2、R3And R4Each independently represents an aromatic group having an electron donating property or neutrality containing n benzene rings and/or aromatic heterocyclic rings, or represents an H atom. The aromatic group with electron donating property or neutrality can be substituted or unsubstituted monocyclic aromatic hydrocarbon or substituted or unsubstituted polycyclic aromatic hydrocarbon; the polycyclic aromatic hydrocarbon can be poly-benzene aliphatic hydrocarbon, biphenyl polycyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon. And n represents 1, 2, 3, 4, 5, 6 or 7.
In the general formula I, R1、R2、R3And R4The groups represented by each may all be the same but not simultaneously H atoms, or any two of the groups may be the same, or any three of the groups may be the same, or four of the groups may be different.
As a specific embodiment of the invention, in the general formula I, R1～R4Any one of the groups represents an aromatic group having electron donating property or neutrality and containing n benzene rings and/or aromatic heterocyclic rings, and the remaining three groups are H atoms. Specifically, the method comprises the following steps: r1Represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and R2、R3And R4Are all H atoms; or, R2Represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and R1、R3And R4Are all H atomsA seed; or, R3Represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and R1、R2And R4Are all H atoms; or, R4Represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, and R1、R2And R3Are all H atoms.
As a specific embodiment of the invention, in the general formula I, R1～R4Any two of the groups represent aromatic groups with electron donating property or neutrality, which contain n benzene rings and/or aromatic heterocyclic rings, and the other two groups are H atoms. Specifically, the method comprises the following steps: r1、R2Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R2The radicals represented may be identical or different and R3And R4Are all H atoms; or, R1、R3Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R3The radicals represented may be identical or different and R2And R4Are all H atoms; or, R1、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R4The radicals represented may be identical or different and R2And R3Are all H atoms; or, R2、R3Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R2、R3The radicals represented may be identical or different and R1And R4Are all H atoms; or, R2、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R2、R4The radicals represented may be identical or different and R1And R3Are all H atoms; or, R3、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R3、R4The radicals represented may be identical or different and R1And R2Are all H atoms.
As a specific embodiment of the invention, in the general formula I, R1～R4Any three of the groups represent an aromatic group having electron donating property or neutrality, which contains n benzene rings and/or aromatic heterocyclic rings, and the remaining one group is an H atom. Specifically, the method comprises the following steps: r1、R2、R3Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R2、R3The radicals represented are identical, any two are identical or different and R is4Is an H atom; or, R1、R2、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R2、R4The radicals represented are identical, any two are identical or different and R is3Is an H atom; or, R1、R3、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R1、R3、R4The radicals represented are identical, any two are identical or different and R is2Is an H atom; or, R3、R3、R4Each independently represents an aromatic group containing n benzene rings and/or aromatic heterocyclic rings, R3、R3、R4The radicals represented are identical, any two are identical or different and R is1Is an H atom.
As a specific embodiment of the invention, in the general formula I, R1、R2、R3And R4Each independently represents an aromatic group having an electron donating property or being neutral, which contains n benzene rings and/or aromatic heterocyclic rings. Wherein R is1、R2、R3、R4Each of the groups represented by may be the same or any two of them may be the same (e.g., R)1、R2Is the same as R3、R4Are each different, or R1、R3Is the same as R2、R4Are each different, or R1、R4Is the same as R2、R3Are each different, or R2、R3Is the same as R1、R4Are each different, or R2、R4Is the same as R1、R3Are each different, or R3、R4Is the same as R1、R2Respectively different), or any three of the same (e.g.: r1、R2、R3Is the same as R4Is different from, or R1、R2、R4Is the same as R3Is different from, or R1、R3、R4Is the same as R2Is different from, or R2、R3、R4Is the same as R1Different), or the four groups may be different from each other.
When R is1、R2、R3And/or R4When the substituted aryl group represents an aromatic group with electron donating property or neutral containing n benzene rings and/or aromatic heterocyclic rings, the respective substituted positions are shown as formula I'.
Figure BDA0002201602140000031
Specifically, the method comprises the following steps:
R1h atoms at any one, two, three or four positions of a1, a2, A3 and a4 which may be substituted for the benzene ring a; preferably, R1H atom substituted for any one of A1, A2, A3 and A4 of benzene ring A; more preferably, R1A H atom at the A1 position, the A2 position or the A3 position of the substituted benzene ring A.
R2H atoms at any one, two, three or four positions of B1, B2, B3 and B4 which may be substituted for a benzene ring B; preferably, R2H atom substituted for any one of positions B1, B2, B3 and B4 of a benzene ring B; more preferably, R2A H atom at the B1 position, the B2 position or the B3 position of the benzene ring B.
R3H atoms at any one, two, three or four positions of C1, C2, C3 and C4 which can substitute benzene ring C; preferably, R3H atom substituted for any one of C1, C2, C3 and C4 of benzene ring C; more preferably, R3A H atom at the C1 position, C2 position or C3 position of the substituted benzene ring C.
R4Any one of D1, D2, D3 and D4 which may be substituted for the benzene ring DH atoms in two, three or four positions; preferably, R4An H atom at any one position of D1, D2, D3 and D4 in place of the benzene ring D; more preferably, R4A H atom at the D1 position, D2 position or D3 position of the substituted benzene ring D.
As a preferred embodiment of the present invention, R1Represents an aromatic group having electron donating property or neutrality containing n benzene rings and/or aromatic heterocyclic rings, which substitutes for the H atom at the A1, A2 or A3 position of the benzene ring A, and R is2、R3And R4All represent H atoms.
As a preferred embodiment of the present invention, R2Represents an aromatic group having electron donating property or neutrality containing n benzene rings and/or aromatic heterocyclic rings, which substitutes for the H atom at the B1, B2 or B3 position of the benzene ring B, and R is1、R3And R4All represent H atoms.
As a preferred embodiment of the present invention, R1、R2Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1Substituted for H atom at position A2 and R2H atom substituted in position B2, R3And R4All represent H atoms. Wherein R is1、R2The groups represented by each may be the same or different.
As a preferred embodiment of the present invention, R1、R3Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1Substituted for H atom at position A1 and R3H atom substituted at position C1, or R1Substituted for H atom at position A2 and R3H atom substituted at position C2, or R1Substituted for H atom at position A3 and R3H atom substituted at position C3, R2And R4All represent H atoms. Wherein R is1、R3The groups represented by each may be the same or different.
As a preferred embodiment of the present invention, R2、R4Each independently represents an electron donating property containing n benzene rings and/or aromatic heterocyclic ringsOr a neutral aromatic radical, R2Substituted for H atom at position B2 and R4H atom substituted in position D2, R1And R3All represent H atoms. Wherein R is2、R4The groups represented by each may be the same or different.
As a preferred embodiment of the present invention, R1、R2、R3And R4Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1H atom substituted at A2 position, R2H atom substituted at position B2, R3Substituted H atom at C2 position and R4An H atom substituted at position D2; or, R1H atom substituted at A2 position, R2H atom substituted at position B1, R3Substituted H atom at C2 position and R4Instead of the H atom in position D1. Wherein R is1、R2、R3、R4Each of the groups represented by may be the same or any two of them may be the same (e.g., R)1、R2Is the same as R3、R4Are each different, or R1、R3Is the same as R2、R4Are each different, or R1、R4Is the same as R2、R3Are each different, or R2、R3Is the same as R1、R4Are each different, or R2、R4Is the same as R1、R3Are each different, or R3、R4Is the same as R1、R2Respectively different), or any three of the same (e.g.: r1、R2、R3Is the same as R4Is different from, or R1、R2、R4Is the same as R3Is different from, or R1、R3、R4Is the same as R2Is different from, or R2、R3、R4Is the same as R1Different), or the four groups may be different from each other.
The invention optimizes the aromatic group with electron donating property or neutrality, which contains n benzene rings and/or aromatic heterocyclic rings, so as to further improve the comprehensive performance of the material. Specifically, the method comprises the following steps:
the aromatic group having an electron donating property or being neutral, which contains n benzene rings and/or aromatic heterocyclic rings, is preferably the following group:
Figure BDA0002201602140000041
Figure BDA0002201602140000051
the aromatic group having an electron donating property or being neutral, which contains n benzene rings and/or aromatic heterocyclic rings, is more preferably the following group:
Figure BDA0002201602140000052
Figure BDA0002201602140000061
the aromatic group having an electron donating property or being neutral, which contains n benzene rings and/or aromatic heterocyclic rings, is further preferably the following group:
Figure BDA0002201602140000062
as described above
Figure BDA0002201602140000063
In the group, W1、W2Each independently represents a straight-chain alkane of C1-C5; the W is1、W2May be the same or different.
In each of the above-mentioned substituent groups,
Figure BDA0002201602140000064
or "- - -" represents a substituted position.
The invention further preferably selects the compounds shown in the general formula I from the compounds shown in the formulas I-1 to I-186.
The organic compound takes a spiro structure as a main body, the main body structure has a rigid structure and an electron-rich structural unit, excellent hole transport performance can be provided, and meanwhile, the thermal stability is good, the structure has proper HOMO and LUMO energy levels and higher Eg, and the photoelectric performance and the service life of an OLED device can be effectively improved. An electron-donating group or a neutral group is introduced into the structure, so that the organic light-emitting diode can be well applied to OLED devices and used as a hole transport material.
The invention also provides a preparation method of the organic compound shown in the general formula I.
1) When R is1、R2、R3And R4In the case of groups with electron-donating properties (such as aromatic amines), the reaction sequence of the preparation process is as follows:
Figure BDA0002201602140000071
starting from bromospiro compound M, with
Figure BDA0002201602140000072
Coupling reaction is carried out to obtain the final target compound I.
The specific preparation method comprises the following steps:
taking toluene as a solvent, palladium acetate and tri-tert-butylphosphine as catalysts, potassium tert-butoxide as an alkali, under the protection of nitrogen and at a temperature of 80-120 ℃, bromizing a spiro compound M and reacting
Figure BDA0002201602140000073
Coupling reaction is carried out to obtain the final target compound I.
2) When R is1、R2、R3And R4In the case of neutral groups, the reaction scheme of the preparation method is as follows:
Figure BDA0002201602140000074
using bromospiro compound M as initial material and boric acid of neutral aromatic ring
Figure BDA0002201602140000075
Coupling reaction is carried out to obtain the final target compound I.
The specific preparation method comprises the following steps:
taking a compound M as an initial raw material, toluene as a solvent, Pd132 as a catalyst, sodium carbonate as an alkali, and controlling the temperature of 70-100 ℃ under the protection of nitrogen
Figure BDA0002201602140000076
Coupling reaction is carried out to obtain the compound I.
The above steps can be carried out by a person skilled in the art by known and conventional means, such as selecting a suitable catalyst, solvent, determining a suitable reaction temperature, time, etc., and the present invention is not limited thereto. The above solvents, catalysts, bases and the like can be synthesized by published commercial methods or methods known in the art.
The invention further provides application of the organic compound shown in the general formula I in an organic electroluminescent device. The organic compound is preferably used as a hole transport material of a hole transport layer in an organic electroluminescent device. The thickness of the hole transport layer may be 10 to 50nm, preferably 20 to 33 nm.
In a preferred embodiment of the present invention, the organic electroluminescent device comprises, in order from bottom to top, a transparent substrate, an anode layer, a hole transport layer made of an organic compound represented by formula I, an electroluminescent layer, an electron transport layer, an electron injection layer, and a cathode layer.
The novel OLED material provided by the invention takes a compound with a spiro structure as a parent nucleus, takes an aromatic compound as an end group, and introduces an electron-donating group with a hole transport property at the active position of the spiro compound to obtain the novel OLED material with the hole transport property. The material has high hole mobility, good film stability, proper molecular energy level and high luminous efficiency, and can be applied to the field of organic electroluminescence and used as a hole transport material.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Figure BDA0002201602140000081
Synthesis of (Compound I-5)
The synthetic route is as follows:
Figure BDA0002201602140000082
the method comprises the following specific steps:
a1 liter three-necked flask was magnetically stirred, and after argon replacement, potassium tert-butoxide (36.2g, 0.376mol), di (4-tolyl) amine (41.37g, 0.21mol, 99% purity) and 100ml of toluene were added in this order. After argon replacement again, 3.4ml of tri-tert-butylphosphine and 0.5g of palladium acetate were added in this order. After the addition, the temperature was raised to 85 ℃. A solution consisting of (57.0g, 0.1mol, 99% purity) M1 and 100ml toluene was initially added dropwise, the temperature being controlled between 80 and 120 ℃. Cooling to 50 deg.C, adding 100ml deionized water, hydrolyzing, stirring for 10 min, filtering, boiling the filter cake with DMF for several times, and rotary steaming to obtain 68.23g white solid with purity of 99.5% and yield of about 85%.
Product MS (m/e): 802.30, respectively; elemental analysis (C)57H42N2OS): theoretical value C: 85.25%, H: 5.27%, N: 3.49%, O: 1.99%, S: 3.99 percent; found value C: 85.25%, H: 5.27%, N: 3.49%, O: 1.99%, S: 3.99 percent.
Example 2
Figure BDA0002201602140000083
Synthesis of (Compound I-44)
The synthetic route is as follows:
Figure BDA0002201602140000091
the method comprises the following specific steps:
A1L three-necked flask was stirred with magnetic stirring and then replaced with argon, followed by addition of potassium tert-butoxide (36.2g, 0.376mol), 4-tolyl-2-naphthylamine (48.93g, 0.21mol, 99% purity) and 100ml of toluene in this order. After argon replacement again, 3.4ml of tri-tert-butylphosphine and 0.5g of palladium acetate were added in this order. After the addition, the temperature was raised to 85 ℃. A solution consisting of (63.3g, 0.1mol, 99% purity) M2 and 100ml toluene was initially added dropwise, the temperature being controlled between 80 and 120 ℃. Cooling to 50 deg.C, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, boiling the filter cake with DMF for several times, and rotary steaming to obtain 78.79g white solid with purity of 99.5% and yield of about 84%.
Product MS (m/e): 938.22, respectively; elemental analysis (C)63H42N2SSe): theoretical value C: 80.67%, H: 4.50%, N: 2.99%, S: 3.42%, Se: 8.42 percent; found value C: 80.60%, H: 4.54%, N: 3.01%, S: 3.43%, Se: 8.42 percent.
Example 3
Figure BDA0002201602140000092
Synthesis of (Compound I-99)
The synthetic route is as follows:
Figure BDA0002201602140000093
the method comprises the following specific steps:
A1L three-necked flask was stirred with magnetic stirring and then replaced with argon, followed by addition of 19.93g (0.188mol) of sodium carbonate, 9-dimethyl-2-boronic acid (23.8g, 0.1mol, 99% purity) and 100ml of toluene in this order. After argon replacement again, 0.23g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of (49.1g, 0.1mol, 99% purity) M3 and 100ml toluene was initially added dropwise, the temperature being controlled between 75 and 80 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, and boiling the filter cake with DMF several times to obtain 51.34g of white solid with purity of 99.5% and yield of 85%.
Product MS (m/e): 588.21, respectively; elemental analysis (C)44H28O2): theoretical value C: 89.77%, H: 4.79%, O: 5.44 percent; found value C: 89.72%, H: 4.82%, O: 5.46 percent.
The intermediates M1, M2, M3 and the like used in the test process can be purchased from Beijing Yanhuaji union photoelectricity technology Co.
According to the technical solutions of example 1, example 2 and example 3, the other compounds of I-1 to I-186 described above can be synthesized with the following analytical data, simply replacing the corresponding starting materials, without any substantial manipulation:
Figure BDA0002201602140000101
Figure BDA0002201602140000111
Figure BDA0002201602140000121
Figure BDA0002201602140000131
Figure BDA0002201602140000141
Figure BDA0002201602140000151
Figure BDA0002201602140000161
Figure BDA0002201602140000171
Figure BDA0002201602140000181
Figure BDA0002201602140000191
Figure BDA0002201602140000201
Figure BDA0002201602140000211
Figure BDA0002201602140000221
Figure BDA0002201602140000231
Figure BDA0002201602140000241
Figure BDA0002201602140000251
Figure BDA0002201602140000261
Figure BDA0002201602140000271
Figure BDA0002201602140000281
Figure BDA0002201602140000291
example 4: OLED device
The embodiment provides a group of OLED red light devices, and the structure of the device is as follows:
ITO/HATCN(1nm)/HT01(40nm)/I-5(20nm)/EML(30nm)/Bphen(40nm)/LiF(1nm)/Al。
the molecular structure of each functional layer material is as follows:
Figure BDA0002201602140000292
the preparation method comprises the following steps:
(1) carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then evaporating a hole transport layer I-5 at the evaporation rate of 0.1nm/s and the evaporation film thickness of 20 nm;
(3) vacuum evaporating EML (electron-emitting layer) on the hole transport layer as the light-emitting layer of the device, wherein the EML comprises a host material and a dye material, and adjusting the host material PR by using a multi-source co-evaporation methodH01 evaporation rate of 0.1nm/s, dye material Ir (piq)2The acac concentration is 5%, and the total film thickness of evaporation plating is 30 nm;
(4) bphen is used as a contrast material of an electron transport layer material of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 30 nm;
(5) LiF with the thickness of 0.5nm is sequentially vacuum-evaporated on the electron transport layer to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
And (3) respectively replacing I-5 in the step (2) with I-44, I-73, I-89, I-99, I-103, I-146, I-170 and I-186 according to the same steps to respectively obtain the OLED-2-OLED-9 provided by the invention.
Following the same procedure as above, only I-5 in step (2) was replaced with NPB (comparative compound), giving comparative example OLED-10 provided by the present invention. The NPB structure is specifically as follows:
Figure BDA0002201602140000301
the performance of the obtained devices OLED-1 to OLED-10 is detected, and the detection results are shown in Table 1.
Table 1: performance test result of OLED device
Figure BDA0002201602140000302
From the above, the devices OLED-1 to OLED-9 prepared by using the organic material shown in formula I provided by the invention have higher current efficiency, and under the condition of the same brightness, the working voltage is obviously lower than that of the device OLED-10 using NPB as the hole transport material, so that the organic material is a hole transport material with good performance.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (17)

1. A novel heterocyclic spiro-structured compound is characterized by having a structure shown as a general formula I:
Figure FDA0002959197930000011
in the general formula I, E1、E2Each independently represents O, S or a Se atom, and the two are different; r1、R2、R3、R4Each independently represents an aromatic group having electron donating properties or being neutral, containing n benzene rings and/or aromatic heterocyclic rings, or represents an H atom;
wherein R is1、R2、R3And R4The groups represented by each may be the same but not simultaneously H atoms, or any three of the groups may be the same, or any two of the groups may be the same, or four of the groups may be different;
the aromatic group containing n benzene rings and/or aromatic heterocyclic rings and having electron donating property or neutrality is the following group:
Figure FDA0002959197930000012
as described above
Figure FDA0002959197930000013
In the group, W1、W2Each independently represents a linear alkane of C1-C5; the W is1、W2May be the same or different.
2. A compound according to claim 1, wherein in formula I, R is1～R4Any one of the groups represents an aromatic ring having an electron donating property or neutral property and containing n benzene rings and/or aromatic heterocyclic ringsAromatic group, the other three groups are H atoms; or R1～R4Any two groups represent aromatic groups which contain n benzene rings and/or aromatic heterocyclic rings and have electron donating property or neutrality, and the other two groups are H atoms; or R1～R4Any three groups represent aromatic groups which contain n benzene rings and/or aromatic heterocyclic rings and have electron donating property or neutrality, and the rest groups are H atoms; or R1、R2、R3And R4Each independently represents an aromatic group having an electron donating property or being neutral, which contains n benzene rings and/or aromatic heterocyclic rings.
3. A compound according to claim 1 or 2, wherein when R is1、R2、R3And/or R4When the substituted aryl group represents an aromatic group with electron donating property or neutral containing n benzene rings and/or aromatic heterocyclic rings, the respective substituted positions are shown as formula I':
Figure FDA0002959197930000021
wherein the content of the first and second substances,
R1h atoms at any one, two, three or four positions of A1, A2, A3 and A4 of the substituted benzene ring A;
R2h atoms at any one, two, three or four positions of B1, B2, B3 and B4 of a substituted benzene ring B;
R3h atoms at any one, two, three or four positions of C1, C2, C3 and C4 of substituted benzene ring C;
R4h atoms at any one, two, three or four positions of D1, D2, D3 and D4 of the substituted benzene ring D.
4. A compound of claim 3, wherein R is1A H atom at any one of A1, A2, A3 and A4 in the substituted benzene ring A.
5. A compound of claim 4, wherein R is1A H atom at the A1 position, the A2 position or the A3 position of the substituted benzene ring A.
6. A compound of claim 3, wherein R is2H atom at any position of B1, B2, B3 and B4 of the substituted benzene ring B.
7. A compound of claim 6, wherein R is2A H atom at the B1 position, the B2 position or the B3 position of the benzene ring B.
8. A compound of claim 3, wherein R is3H atom at any position of C1, C2, C3 and C4 of substituted benzene ring C.
9. A compound of claim 8, wherein R is3A H atom at the C1 position, C2 position or C3 position of the substituted benzene ring C.
10. A compound of claim 3, wherein R is4A H atom at any one of positions D1, D2, D3 and D4 in the substituted benzene ring D.
11. The compound of claim 10, wherein R is4A H atom at the D1 position, D2 position or D3 position of the substituted benzene ring D.
12. A compound of claim 3, wherein R is1Represents an aromatic group having electron donating property or neutrality containing n benzene rings and/or aromatic heterocyclic rings, which substitutes for the H atom at the A1, A2 or A3 position of the benzene ring A, and R is2、R3And R4All represent H atoms;
or, R2Represents an aromatic group having electron donating property or neutrality and containing n benzene rings and/or aromatic heterocyclic rings, which is substituted for the positions B1 and B2 of the benzene ring BOr H atom in position B3, and R1、R3And R4All represent H atoms.
13. A compound of claim 3, wherein R is1、R2Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1H atom substituted at position A2, and R2H atom substituted in position B2, R3And R4All represent H atoms; wherein R is1、R2The groups represented by each may be the same or different;
or, R1、R3Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1Substituted for H atom at position A1 and R3H atom substituted at position C1, R2And R4All represent H atoms; wherein R is1、R3The groups represented by each may be the same or different;
or, R1、R3Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1Substituted for H atom at position A2 and R3H atom substituted at position C2, R2And R4All represent H atoms; wherein R is1、R3The groups represented by each may be the same or different;
or, R1、R3Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1Substituted for H atom at position A3 and R3H atom substituted at position C3, R2And R4All represent H atoms; wherein R is1、R3The groups represented by each may be the same or different;
or, R2、R4Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R2Substituted for H atom at position B2 and R4H atom substituted in position D2, R1And R3All represent H atoms; wherein R is2、R4The groups represented by each may be the same or different.
14. A compound of claim 3, wherein R is1、R2、R3And R4Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1H atom substituted at A2 position, R2H atom substituted at position B2, R3Substituted H atom at C2 position and R4An H atom substituted at position D2; wherein R is1、R2、R3、R4The groups represented by each may be the same, or any two of them may be the same, or any three may be the same, or four may be different;
or, R1、R2、R3And R4Each independently represents an aromatic group having electron donating property or neutral property containing n benzene rings and/or aromatic heterocyclic rings, R1H atom substituted at A2 position, R2H atom substituted at position B1, R3Substituted H atom at C2 position and R4An H atom substituted at position D1; wherein R is1、R2、R3、R4The groups represented by each may all be the same, or any two of them may be the same, or any three of them may be the same, or four of them may be different from each other.
15. The compound of claim 1, selected from the group consisting of:
Figure FDA0002959197930000041
Figure FDA0002959197930000051
Figure FDA0002959197930000061
Figure FDA0002959197930000071
Figure FDA0002959197930000081
Figure FDA0002959197930000091
Figure FDA0002959197930000101
Figure FDA0002959197930000111
Figure FDA0002959197930000121
Figure FDA0002959197930000131
Figure FDA0002959197930000141
Figure FDA0002959197930000151
Figure FDA0002959197930000161
Figure FDA0002959197930000171
16. use of a compound according to any one of claims 1 to 15 in an organic electroluminescent device.
17. Use according to claim 16, wherein the compound is used as a hole transport material for a hole transport layer in an organic electroluminescent device.
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