CN112480133A - Compound with benzospiroanthracene as core and application thereof - Google Patents

Compound with benzospiroanthracene as core and application thereof Download PDF

Info

Publication number
CN112480133A
CN112480133A CN201910860880.2A CN201910860880A CN112480133A CN 112480133 A CN112480133 A CN 112480133A CN 201910860880 A CN201910860880 A CN 201910860880A CN 112480133 A CN112480133 A CN 112480133A
Authority
CN
China
Prior art keywords
group
general formula
substituted
unsubstituted
benzospiroanthracene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910860880.2A
Other languages
Chinese (zh)
Other versions
CN112480133B (en
Inventor
张小庆
王芳
赵四杰
张兆超
李崇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Sunera Technology Co Ltd
Original Assignee
Jiangsu Sunera Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Sunera Technology Co Ltd filed Critical Jiangsu Sunera Technology Co Ltd
Priority to CN201910860880.2A priority Critical patent/CN112480133B/en
Publication of CN112480133A publication Critical patent/CN112480133A/en
Application granted granted Critical
Publication of CN112480133B publication Critical patent/CN112480133B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • 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
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a compound taking benzospiroanthracene as a core and application thereof, and the structure of the organic compound provided by the invention is shown as a general formula (1).
Figure DDA0002199718210000011
The compound provided by the invention has higher glass transition temperature and molecular weightThe Organic Light Emitting Diode (OLED) device has the advantages of high sub-thermal stability, proper HOMO and LUMO energy levels, and capability of effectively improving the photoelectric property of the OLED device and prolonging the service life of the OLED device through optimization of the structure of the device.

Description

Compound with benzospiroanthracene as core and application thereof
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a compound taking benzospiroanthracene as a core and application thereof in an organic electroluminescent device.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In order to solve the problems in the prior art, the applicant of the present invention provides a compound with benzospiroanthracene as a core and an application thereof. The compound takes benzospiroanthracene as a core, has higher glass transition temperature and molecular thermal stability, and appropriate HOMO and LUMO energy levels, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows: a compound taking benzospiroanthracene as a core has a structure shown as a general formula (1):
Figure BDA0002199718190000021
in the general formula (1), the dotted line indicates that two groups are linked or not;
R1、R2、R3、R4each independently represents a hydrogen atom, a cyano group, a halogen atom, C1-20Alkyl, phenyl, naphthyl, biphenyl, naphthyridinyl, pyridyl, a structure represented by general formula (2) or general formula (3), and R1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
wherein m, n, p and q are integers which are not less than 0, and m + n + p + q is 1, 2 or 3;
Figure BDA0002199718190000022
in the general formulae (2) and (3), R5、R6Each independently represents a structure represented by the general formula (4) or the general formula (5)
Figure BDA0002199718190000023
L1、L2Each independently represents a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
x in the general formula (3) represents-O-, -S-, -C (R)7)(R8) -or-N (R)9)-；
X in the general formula (4)1、X2Each independently represents a single bond, -O-, -S-, -C (R)10)(R11) -or-N (R)12) -; and X1、X2Not simultaneously represent a single bond;
the R is7～R12Each independently is represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms; and R is7And R8、R10And R11Do not form a ring or bond to each other to form a ring;
the general formula (4) and the general formula (5) are connected with the two adjacent positions marked by the marks in the general formula (2) or the general formula (3) in a ring-by-ring mode;
the above-mentioned substituent for the substitutable group is optionally selected from the group consisting of a deuterium atom, a halogen atom, a cyano group, and C1-20Alkyl of (C)6-30Aryl, 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatoms in the heteroarylene and heteroaryl groups are selected from one or more of N, O or S.
As a further improvement of the present invention, in the general formula (1), the dotted line indicates that two groups are connected or not connected by a single bond.
As a further improvement of the invention, R is7And R8、R10And R11Not forming a ring or being bonded to each other by a single bond.
As a further improvement of the invention, R is1、R2、R3、R4Independently represent a structure represented by a general formula (2) or a general formula (3), and m, n, p and q are respectively 0 or 1.
As a further improvement of the invention, R is1、R2、R3、R4Each independently represents a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a biphenyl group, a naphthyridinyl group, a pyridyl group, a structure represented by general formula (2) or general formula (3), and R1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
said L1、L2Represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene;
the R is7～R12Each independently represents methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclohexyl, substituted orOne of unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and substituted or unsubstituted pyridyl;
the substituent when each of the above groups is substituted is one or more selected from the group consisting of a deuterium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a biphenyl group, a naphthyl group, a furyl group, a carbazolyl group, a thienyl group and a pyridyl group.
As a further improvement of the invention, said C6-30The arylene group of (a) is represented by phenylene, naphthylene, biphenylene;
the 5-30-membered heteroarylene group is represented by one of pyridylene group, carbazolyl group, furylene group, pyrimidylene group, pyrazinylene group, pyridazinylene group, dibenzofuranylene group, 9-dimethylfluorenyl group, N-phenylcarbazolyl group, quinolylene group, isoquinolylene group and naphthyridine group;
said C is1-20The alkyl is one of methyl, ethyl, isopropyl and tert-butyl;
said C is6-30The aryl group is one of phenyl, naphthyl, biphenyl, terphenyl and anthryl;
the 5-30-membered heteroaryl is represented by one of pyridyl, carbazolyl, furyl, pyrimidinyl, pyrazinyl, pyridazinyl, thienyl, dibenzofuryl, 9-dimethylfluorenyl, N-phenylcarbazolyl, quinolyl, isoquinolyl, naphthyridinyl, oxazolyl, imidazolyl, benzoxazolyl and benzimidazolyl.
As a further improvement of the invention, R is2The structure is represented by a general formula (2) or a general formula (3).
As a further improvement of the invention, R is3The structure is represented by a general formula (2) or a general formula (3).
As a further improvement of the present invention, the general formula (1) is any one of the following specific compounds:
Figure BDA0002199718190000031
Figure BDA0002199718190000041
Figure BDA0002199718190000051
Figure BDA0002199718190000061
Figure BDA0002199718190000071
Figure BDA0002199718190000081
Figure BDA0002199718190000091
Figure BDA0002199718190000101
Figure BDA0002199718190000111
Figure BDA0002199718190000121
an organic electroluminescent device, wherein a plurality of organic thin film layers are arranged between an anode and a cathode of the organic electroluminescent device, and at least one organic thin film layer contains the compound taking benzospiroanthracene as a core.
Further, the multilayer organic thin film layer includes an electron blocking layer and/or a hole transporting layer containing the benzospiroanthracene-based compound.
A display element comprising the organic electroluminescent device.
The invention also relates to an application of the compound taking benzospiroanthracene as a core in preparing an organic electroluminescent device,
compared with the prior art, the invention has the beneficial technical effects that:
(1) the compound takes benzospiroanthracene as a core, is connected with an electron-donating group, has higher hole mobility, and can be used as a material of a hole transport layer of an OLED light-emitting device to improve the recombination efficiency of excitons in a light-emitting layer and improve the energy utilization rate, thereby improving the light-emitting efficiency of the device.
(2) The compound of the invention ensures that the distribution of electrons and holes in the luminescent layer is more balanced, and under the proper HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; can effectively improve the exciton utilization rate, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
(3) The compound has higher Tg temperature and smaller intermolecular force. The compound has lower evaporation temperature due to smaller intermolecular force, thereby not only ensuring that the evaporation material is not decomposed for a long time in mass production, but also reducing the deformation influence of heat radiation of the evaporation temperature on the Mask.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is an electron transport or hole blocking layer, 8 is an electron injection layer, and 9 is a cathode layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
All reactants in the following examples were purchased from cigarette Taiwangrun Fine chemical Co., Ltd.
Example 1 synthesis of compound 1:
Figure BDA0002199718190000131
dissolving 0.01mol of reactant A-1 and 0.012mol of reactant B-1 in 150mL of toluene, adding 0.015mol of potassium tert-butoxide, reacting at 120 ℃ for 24 hours in the atmosphere of nitrogen, sampling a spot plate, cooling and filtering after the reaction is completed, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a compound 1, wherein the yield is 76.85%, and the HPLC purity is 99.65%; elemental analysis Structure (C)47H27NO) theoretical value: c, 90.80; h, 4.38; n, 2.25; test values are: c, 90.81; h, 4.37; and N, 2.27. Hrms (ei): theoretical value is 621.2093, found 621.2033.
Example 15 synthesis of compound 223:
Figure BDA0002199718190000132
0.01mol of the reactant A-4 and 0.012mol of the reactant B-7 were dissolved in 150mL of a mixed solution of toluene/ethanol (V toluene: V ethanol ═ 5: 1), deoxygenated, and then 0.0002mol of Pd (PPh) was added3)4And 0.02mol of K2CO3Reacting at 110 ℃ for 24 hours in the atmosphere of nitrogen, sampling a sample, cooling and filtering after reactants react completely, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a compound 223, wherein the yield is 76.5%, and the HPLC purity is 97.36%; elemental analysis Structure (C)59H36N2) Theoretical value: c, 91.68; h, 4.69; n, 3.62; test values are: c, 91.68; h, 4.68; and N, 3.63. Hrms (ei): theoretical value: 772.2878, found: 772.2856.
the synthesis of compound a-1 in example 1 is as follows:
Figure BDA0002199718190000133
dissolving 0.02mol of raw material C-1 in 60mL of dry THF, preserving heat at-78 ℃ for 30min, adding 24mL of 1.2M n-butyllithium solution in the atmosphere of nitrogen, stirring for 1-2 h, continuously adding 0.02mol of raw material D-1 in the atmosphere of nitrogen, stirring uniformly, slowly raising the temperature to room temperature, continuously stirring for reaction for 10-24 h at room temperature, adding 20mL of water into the reaction system, continuously stirring for 1-2 h, separating out a product from the reaction system, and filtering to obtain an intermediate I-1, wherein the HPLC purity is 92.55%, and the yield is 85.7%; dissolving 0.02mol of intermediate I-1 in a mixed solution of 50mL of acetic acid and 5mL of hydrochloric acid, stirring and heating to 110 ℃, reacting for 10h, naturally cooling to room temperature, separating out a product, filtering, washing with water and methanol to obtain a reactant A-1 with the HPLC purity of 99.29% and the yield of 75.5%; hrms (ei) (high resolution mass spectrometry): theoretical value of 444.0514, found value of 444.0528
The following compounds were synthesized by repeating the preparation procedures of example 1 or example 15; wherein reaction condition I represents the same preparation process as in example 1; reaction condition II means that the preparation process was the same as in example 15; except that the reactants a and B listed in the following table 1-1 were used; the specific synthesis of the reactant A in Table 1-1 was the same as that of the reactant A-1, except that the starting material C and the starting material D were different.
TABLE 1-1
Figure BDA0002199718190000141
Figure BDA0002199718190000151
Figure BDA0002199718190000161
Figure BDA0002199718190000171
Nuclear magnetic data are shown in tables 1-2 below
Figure BDA0002199718190000172
Figure BDA0002199718190000181
The organic compound of the present invention is used in a light-emitting device, and can be used as an electron blocking layer or a hole transport layer material. The T1 level, thermal property, HOMO level and mobility were measured for compounds 1, 13, 29, 57, 72, 98, 114, 133, 155, 170, 173, 190, 202, 214, 223, 228, 250, 252, 269, 277, 289, 305, 312 and 318 of the present invention, respectively, and the results are shown in table 2.
TABLE 2
Compound (I) T1(eV) Tg(℃) Td(℃) HOMO energy level (eV) Mobility (cm 2/(V.s))
1 2.68 150 418 5.68 3.40E-04
13 2.58 148 418 5.54 3.90E-04
29 2.69 151 414 5.65 3.90E-04
57 2.71 155 429 5.67 1.80E-04
72 2.63 153 420 5.52 1.90E-04
98 2.69 160 412 5.66 9.50E-04
114 2.59 146 425 5.54 7.10E-04
133 2.66 146 420 5.68 3.30E-04
155 2.73 155 414 5.72 1.90E-04
170 2.66 151 430 5.67 2.50E-04
173 2.63 151 426 5.5 1.00E-04
179 2.69 150 419 5.69 3.00E-04
190 2.52 150 430 5.52 5.70E-04
202 2.58 146 410 5.52 1.30E-04
214 2.58 146 426 5.53 5.40E-04
223 2.65 157 427 5.52 5.40E-04
228 2.59 152 419 5.55 1.20E-04
250 2.72 150 426 5.69 2.80E-04
252 2.72 153 428 5.68 1.20E-04
269 2.66 159 426 5.69 7.90E-04
277 2.56 149 415 5.54 9.00E-04
289 2.72 159 416 5.73 3.70E-04
305 2.62 145 423 5.52 1.90E-04
312 2.69 145 411 5.74 4.40E-04
317 2.74 145 413 5.65 3.90E-04
318 2.67 148 428 5.65 2.50E-04
Note: the triplet energy level T1 was measured by Fluorolog-3 series fluorescence spectrometer from Horiba under the conditions of 2 x 10-5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermal weight loss temperature Td is 1% weight loss in a nitrogen atmosphereTemperature, measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and nitrogen flow rate of 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS-3), which is an atmospheric environment. Hole mobility: the material was fabricated into single charge devices and tested by the SCLC method.
As can be seen from the data in table 2, the organic compound of the present invention has a suitable HOMO energy level and can be applied to a hole transport layer, and the organic compound containing the benzospiroanthracene as a core of the present invention has a high hole mobility energy level and a high thermal stability, so that the efficiency and the lifetime of the manufactured OLED device containing the organic compound of the present invention are both improved.
The effect of the use of the synthesized compound of the present invention as a hole transport and/or electron blocking material in a device is explained in detail below by device examples 1 to 26 and device comparative example 1. Device examples 2 to 26 and device comparative example 1 compared with device example 1, the manufacturing processes of the devices were completely the same, and the same substrate material and electrode material were used, and the film thicknesses of the electrode materials were also kept the same, except that the materials of the hole transport layer or the electron blocking layer in the devices were changed. The device stack structure is shown in table 3, and the performance test results of each device are shown in tables 4 and 5.
Device example 1
The preparation process comprises the following steps:
as shown in FIG. 1, the transparent substrate layer 1 is formed by washing the ITO anode layer 2 (having a film thickness of 150nm), i.e., sequentially performing alkali washing, pure water washing, drying, and ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, HT-1 and P-1 having a film thickness of 10nm were deposited as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 98: 2. Then, compound 13 was evaporated to a thickness of 55nm as a hole transport layer 4. EB-1 was then evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that BH used by the OLED light emitting layer 6 is used as a main material, BD is used as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light emitting layer is 20 nm. After the light-emitting layer 6, ET-1 and Liq were continuously vacuum-evaporated, the mass ratio of ET-1 to Liq was 1:1, the film thickness was 35nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a Yb layer having a film thickness of 1nm, which is an electron-injecting layer 8, was formed by a vacuum evaporation apparatus. On the electron injection layer 8, a vacuum deposition apparatus was used to produce an Mg: the Ag electrode layer is a cathode layer 9, and the mass ratio of Mg to Ag is 1: 9.
After the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the current efficiency, the light emission spectrum, and the lifetime of the device were measured. The structures of device examples 2 to 24 and device comparative example 1 prepared in the same manner are shown in table 3; the current efficiency, color and LT95 lifetime test results at 1000nits luminance of the resulting devices are shown in table 4. The molecular structural formula of the related material is shown as follows:
Figure BDA0002199718190000201
TABLE 3
Figure BDA0002199718190000202
Figure BDA0002199718190000211
Figure BDA0002199718190000221
The efficiency and lifetime data for each device example and device comparative example 1 are shown in table 4.
TABLE 4
Figure BDA0002199718190000222
Figure BDA0002199718190000231
As can be seen from the device data results of table 4, the organic light emitting device of the present invention achieves a greater improvement in both efficiency and lifetime over OLED devices of known materials.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A compound with benzospiroanthracene as a core is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0002199718180000011
in the general formula (1), the dotted line indicates that two groups are linked or not;
R1、R2、R3、R4each independently represents a hydrogen atom, a deuterium atom, a cyano group, a halogen, C1-20Alkyl, phenyl, naphthyl, biphenyl, naphthyridinyl, pyridyl, a structure represented by general formula (2) or general formula (3), and R1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
wherein m, n, p and q are integers which are not less than 0, and m + n + p + q is 1, 2 or 3;
Figure FDA0002199718180000012
in the general formulae (2) and (3), R5、R6Each independently represents a structure represented by a general formula (4) or a general formula (5);
Figure FDA0002199718180000013
L1、L2each independently represents a single bond, substituted or unsubstituted C6-30Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
x in the general formula (3) represents-O-, -S-, -C (R)7)(R8) -or-N (R)9)-；
X in the general formula (4)1、X2Each independently represents a single bond, -O-, -S-, -C (R)10)(R11) -or-N (R)12) -; and X1、X2Not simultaneously represent a single bond;
the R is7～R12Each independently is represented by C1-20Alkyl, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms; and R is7And R8、R10And R11Do not form a ring or bond to each other to form a ring;
the general formula (4) and the general formula (5) are connected with the two adjacent positions marked by the marks in the general formula (2) or the general formula (3) in a ring-by-ring mode;
the above-mentioned substituent for the substitutable group is optionally selected from the group consisting of a deuterium atom, a halogen atom, a cyano group, and C1-20Alkyl of (C)6-30Aryl, 5-30 membered heteroaryl containing one or more heteroatoms;
the heteroatoms in the heteroarylene and heteroaryl groups are selected from one or more of N, O or S.
2. The benzospiroanthracene-based compound according to claim 1, wherein R is1、R2、R3、R4Independently represent a structure represented by a general formula (2) or a general formula (3), and m, n, p and q are respectively 0 or 1.
3. The benzospiroanthracene nucleus of claim 1A cardiac compound characterized in that R is1、R2、R3、R4Each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a biphenyl group, a naphthyridinyl group, a pyridyl group, a structure represented by the general formula (2) or the general formula (3), and R1、R2、R3、R4At least one of the structures is represented by a general formula (2) or a general formula (3);
said L1、L2Each independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted biphenylene group;
the R is7～R12Each independently represents one of methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted pyridyl;
the substituent when each of the above groups is substituted is one or more selected from the group consisting of a deuterium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, a biphenyl group, a naphthyl group, a furyl group, a carbazolyl group, a thienyl group and a pyridyl group.
4. The benzospiroanthracene-based compound according to claim 1, wherein R is2The structure is represented by a general formula (2) or a general formula (3).
5. The benzospiroanthracene-based compound according to claim 1, wherein R is3The structure is represented by a general formula (2) or a general formula (3).
6. The benzospiroanthracene-based compound according to claim 1, wherein the general formula (1) is any one of the following specific compounds:
Figure FDA0002199718180000021
Figure FDA0002199718180000031
Figure FDA0002199718180000041
Figure FDA0002199718180000051
Figure FDA0002199718180000061
Figure FDA0002199718180000071
Figure FDA0002199718180000081
Figure FDA0002199718180000091
Figure FDA0002199718180000101
Figure FDA0002199718180000111
7. an organic electroluminescent device comprising a plurality of organic thin film layers between an anode and a cathode, wherein at least one of the organic thin film layers contains the benzospiroanthracene-based compound according to any one of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, wherein the multilayer organic thin film layer comprises an electron blocking layer and/or a hole transporting layer containing the benzospiroanthracene-based compound according to any one of claims 1 to 6.
9. A display element comprising the organic electroluminescent device according to any one of claims 7 to 8.
10. Use of a benzospiroanthracene-based compound according to any one of claims 1 to 6 for the preparation of an organic electroluminescent device.
CN201910860880.2A 2019-09-11 2019-09-11 Compound with benzospiroanthracene as core and application thereof Active CN112480133B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910860880.2A CN112480133B (en) 2019-09-11 2019-09-11 Compound with benzospiroanthracene as core and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910860880.2A CN112480133B (en) 2019-09-11 2019-09-11 Compound with benzospiroanthracene as core and application thereof

Publications (2)

Publication Number Publication Date
CN112480133A true CN112480133A (en) 2021-03-12
CN112480133B CN112480133B (en) 2023-08-08

Family

ID=74920348

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910860880.2A Active CN112480133B (en) 2019-09-11 2019-09-11 Compound with benzospiroanthracene as core and application thereof

Country Status (1)

Country Link
CN (1) CN112480133B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950763A (en) * 2019-11-04 2020-04-03 苏州久显新材料有限公司 Spirobenzanthrone derivatives and electronic devices

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016182270A1 (en) * 2015-05-08 2016-11-17 머티어리얼사이언스 주식회사 Organic electroluminescent device
KR20170049398A (en) * 2015-10-27 2017-05-10 주식회사 엘지화학 Cyclic compound and organic light emitting device comprising the same
CN106699573A (en) * 2015-11-17 2017-05-24 材料科学有限公司 Spiro-typed organic materials and organic electroluminescent device utilizing the same
CN109824522A (en) * 2019-03-29 2019-05-31 吉林奥来德光电材料股份有限公司 A kind of organic luminescent compounds and its preparation method and application
WO2019166269A1 (en) * 2018-02-28 2019-09-06 Novaled Gmbh Spiro benzoanthracene-fluorene derivatives and their use in organic electronic devices, displays and lighting devices
WO2019166270A1 (en) * 2018-02-28 2019-09-06 Novaled Gmbh Organic electronic device, display and lighting devices comprising the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016182270A1 (en) * 2015-05-08 2016-11-17 머티어리얼사이언스 주식회사 Organic electroluminescent device
KR20170049398A (en) * 2015-10-27 2017-05-10 주식회사 엘지화학 Cyclic compound and organic light emitting device comprising the same
CN106699573A (en) * 2015-11-17 2017-05-24 材料科学有限公司 Spiro-typed organic materials and organic electroluminescent device utilizing the same
WO2019166269A1 (en) * 2018-02-28 2019-09-06 Novaled Gmbh Spiro benzoanthracene-fluorene derivatives and their use in organic electronic devices, displays and lighting devices
WO2019166270A1 (en) * 2018-02-28 2019-09-06 Novaled Gmbh Organic electronic device, display and lighting devices comprising the same
CN111788177A (en) * 2018-02-28 2020-10-16 诺瓦尔德股份有限公司 Spirobenzanthracene-fluorene derivatives and their use in organic electronic devices, display and lighting devices
CN109824522A (en) * 2019-03-29 2019-05-31 吉林奥来德光电材料股份有限公司 A kind of organic luminescent compounds and its preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950763A (en) * 2019-11-04 2020-04-03 苏州久显新材料有限公司 Spirobenzanthrone derivatives and electronic devices

Also Published As

Publication number Publication date
CN112480133B (en) 2023-08-08

Similar Documents

Publication Publication Date Title
CN107021926B (en) Compound containing azaspirofluorene and nitrogen-containing six-membered heterocycle and application of compound in OLED
CN107586261B (en) Organic compound containing spiro dibenzosuberene fluorene and application thereof
CN112047873B (en) Compound with triarylamine structure as core and preparation method thereof
CN109928886B (en) Compound containing triarylamine and fluorene and application thereof
CN111675701B (en) Triphenylamine structure-based organic electroluminescent compound and organic electroluminescent device
CN111943941B (en) Compound with xanthone as core and application thereof
CN111662190A (en) Organic compound containing pyrene or aza-pyrene and application thereof
CN110885338A (en) Organic compound with triarylamine as core, preparation method and application thereof
CN113004259B (en) Compound with anthrone skeleton as core and application thereof
CN110835318A (en) Organic compound with azafluorene as core and preparation method and application thereof
CN110577523B (en) Compound containing triarylamine structure and organic electroluminescent device prepared from compound
CN110294735B (en) Compound with anthracene and phenanthrene as core and application of compound in organic electroluminescent device
CN110963904A (en) Compound with ketone and fluorene as cores, preparation method and application thereof
CN112479904B (en) Organic compound with indeno-anthracene derivative as core and application thereof
CN112479901B (en) Organic compound with indeno-anthracene derivative as core and application thereof
CN110655486A (en) Compound with dibenzosuberene as core and application thereof
CN110003019B (en) High-mobility organic compound with mesitylene as core and application thereof
CN109912592B (en) Compound containing pyridoindole and application of compound in organic electroluminescent device
CN112480133B (en) Compound with benzospiroanthracene as core and application thereof
CN111253410A (en) Compound with fluorene as core and application thereof
CN111362959A (en) Compound with olefinic bond-containing fluorene as core and application thereof
CN111362955A (en) Organic compound and application thereof to OLED device
CN110862290A (en) Compound containing anthrene structure and application thereof in organic electroluminescent device
CN112480092B (en) Compound with diphenylacridine as core and application thereof in organic electroluminescent device
CN114621171A (en) Organic compound with naphthalene anthracene derivative as core and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 210 Xinzhou Road, Xinwu District, Wuxi City, Jiangsu Province

Applicant after: Jiangsu March Technology Co.,Ltd.

Address before: 214112 No.210 Xinzhou Road, New District, Wuxi City, Jiangsu Province

Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd.

CB02 Change of applicant information
CB02 Change of applicant information

Address after: No. 2 Fengwei Road, Huizhi Enterprise Center, Xishan Economic and Technological Development Zone, Xishan District, Wuxi City, Jiangsu Province, 214000

Applicant after: Jiangsu March Technology Co.,Ltd.

Address before: 210 Xinzhou Road, Xinwu District, Wuxi City, Jiangsu Province

Applicant before: Jiangsu March Technology Co.,Ltd.

GR01 Patent grant
GR01 Patent grant