CN112480133B - Compound with benzospiroanthracene as core and application thereof - Google Patents
Compound with benzospiroanthracene as core and application thereof Download PDFInfo
- Publication number
- CN112480133B CN112480133B CN201910860880.2A CN201910860880A CN112480133B CN 112480133 B CN112480133 B CN 112480133B CN 201910860880 A CN201910860880 A CN 201910860880A CN 112480133 B CN112480133 B CN 112480133B
- Authority
- CN
- China
- Prior art keywords
- general formula
- benzospiroanthracene
- represented
- compound
- group
- 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.)
- Active
Links
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
Abstract
The invention discloses a compound taking benzo-spiro anthracene as a core and application thereof, and the structure of the organic compound provided by the invention is shown as a general formula (1).The compound provided by the invention has higher glass transition temperature, higher molecular thermal stability and proper HOMO and LUMO energy levels, and can effectively improve the photoelectric property of an OLED device and prolong the service life of the OLED device through device structure optimization.
Description
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 electroluminescent (OLED: organic Light Emission Diodes) device technology can be used for manufacturing novel display products and novel illumination products, is hopeful to replace the existing liquid crystal display and fluorescent lamp illumination, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, wherein various functional materials are mutually overlapped together according to purposes to jointly 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 act through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, so that OLED electroluminescence is generated.
At present, the OLED display technology has been applied to the fields of smart phones, tablet computers and the like, and further expands to the large-size application fields of televisions and the like, but compared with the actual product application requirements, the OLED display technology has the advantages that the luminous efficiency, the service life and the like of the OLED device are further improved. The studies on the improvement of the performance of the OLED light emitting device include: 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 is the innovation of the structure and the manufacturing process of the OLED device needed, but also the continuous research and innovation of the OLED photoelectric functional material are needed, and the functional material of the OLED with higher performance is created.
The OLED photoelectric functional materials applied to the OLED device can be classified into two major categories in terms of use, namely, charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further classified into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further classified into host light emitting materials and doping materials.
In order to manufacture high-performance OLED light emitting devices, 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, and the like, and as a host material of a light emitting layer, a material having good bipolar properties, appropriate HOMO/LUMO energy levels, and the like are required.
The OLED photoelectric functional material film layer forming the OLED device at least comprises more than two layers, and the industrially applied OLED device structure comprises a plurality of film layers such as a hole injection layer, a hole transmission layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transmission layer, an electron injection layer and the like, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transmission material, a luminescent material, an electron transmission material and the like, and the material types and collocation forms 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 be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, the OLED functional material or material combination with high performance must be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In view of the actual demands of the current OLED display lighting industry, the development of OLED materials is far from sufficient, and is in line with the requirements of panel manufacturing enterprises, so that the OLED materials are particularly important as organic functional materials with higher performance for the material enterprises.
Disclosure of Invention
In view of the above problems in the prior art, the applicant provides a compound with benzospiroanthracene as a core and application thereof. The compound takes the benzo-spiro-anthracene as a core, has higher glass transition temperature and molecular thermal stability, is suitable for HOMO and LUMO energy levels, and can effectively improve the photoelectric property of an OLED device and prolong the service life of the OLED device through device structure optimization.
The technical scheme of the invention is as follows: a compound with benzospiroanthracene as a core has a structure shown in a general formula (1):
in the general formula (1), the dotted line indicates that two groups are connected or not connected;
R 1 、R 2 、R 3 、R 4 are independently represented by a hydrogen atom, a cyano group, a halogen, C 1-20 Alkyl, phenyl, naphthyl, biphenyl, naphthyridinyl, pyridyl, a structure of the formula (2) or the formula (3), and R 1 、R 2 、R 3 、R 4 At least one of them is represented by the general formula (2) orA structure represented by the general formula (3);
wherein m, n, p, q is an integer of 0 or more, and m+n+p+q=1, 2 or 3;
in the general formula (2) and the general formula (3), R 5 、R 6 Are respectively and independently represented by a structure shown as a general formula (4) or a general formula (5)
L 1 、L 2 Each independently represented as a single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted 5-30 membered heteroarylene containing one or more heteroatoms;
x in the general formula (3) is represented by-O-, -S-, -C (R) 7 )(R 8 ) -or-N (R) 9 )-；
X in the general formula (4) 1 、X 2 Are each independently represented by a single bond, -O-, -S-, -C (R 10 )(R 11 ) -or-N (R) 12 ) -; and X is 1 、X 2 Not simultaneously denoted as single bond;
the R is 7 ～R 12 Each independently is represented by C 1-20 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted 5-30 membered heteroaryl containing one or more heteroatoms; and R is 7 And R is R 8 、R 10 And R is R 11 Not forming a ring or bonding each other to form a ring;
two adjacent positions marked by the general formula (4) and the general formula (5) are connected with two adjacent positions marked by the general formula (2) or the general formula (3) in a parallel ring mode;
the substituents mentioned above for the substituents which may be substituted are optionally selected from deuterium atom, halogen atom, cyano group, C 1-20 Alkyl, C of (2) 6-30 Aryl, 5-30 membered heteroaryl containing one or more heteroatoms;
the hetero atoms in the heteroarylene and heteroaryl groups are selected from one or more of N, O or S.
As a further development of the invention, in the general formula (1), the dashed line indicates that the two groups are linked or not linked by a single bond.
As a further improvement of the present invention, the R 7 And R is R 8 、R 10 And R is R 11 Not forming a ring or being bonded to each other by a single bond.
As a further improvement of the present invention, the R 1 、R 2 、R 3 、R 4 Each independently represents a structure represented by the general formula (2) or the general formula (3), and m, n, p, q is 0 or 1, respectively.
As a further improvement of the present invention, the R 1 、R 2 、R 3 、R 4 Each independently represents a fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group, naphthyl group, biphenyl group, naphthyridinyl group, pyridyl group, a structure represented by the general formula (2) or the general formula (3), and R 1 、R 2 、R 3 、R 4 At least one of the structures represented by the general formula (2) or the general formula (3);
the L is 1 、L 2 Represented by a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group;
the R is 7 ～R 12 Each independently represents one of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl;
the substituent when each of the above groups is substituted is selected from one or more of deuterium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, cyclohexyl group, phenyl group, biphenyl group, naphthyl group, furyl group, carbazolyl group, thienyl group, or pyridyl group.
As a further improvement of the present invention, the C 6-30 The arylene group of (2) is represented by phenylene,Naphthylene, biphenylene;
the 5-30 membered heteroarylene group is represented by one of a pyridylene group, a carbazolylene group, a furanylene group, a pyrimidinylene group, a pyrazinylene group, a pyridazinylene group, a dibenzofuranylene group, a 9, 9-dimethylfluorenylene group, an N-phenylcarbazolylene group, a quinolinylene group, an isoquinolylene group and a naphthyridineylene group;
the C is 1-20 Alkyl is one of methyl, ethyl, isopropyl and tert-butyl;
the C is 6-30 Aryl of (2) 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, dibenzofuranyl, 9-dimethylfluorenyl, N-phenylcarbazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, oxazolyl, imidazolyl, benzoxazolyl and benzimidazolyl.
As a further improvement of the invention, the R 2 The structure is represented by a general formula (2) or a general formula (3).
As a further improvement of the invention, the R 3 The 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:
/>
/>
/>
an organic electroluminescent device, wherein a plurality of organic film layers are arranged between an anode and a cathode of the organic electroluminescent device, and at least one organic film layer contains the compound taking the benzospiroanthracene as a core.
Further, the multi-layer organic thin film layer comprises an electron blocking layer and/or a hole transporting layer, and the electron blocking layer and/or the hole transporting layer contains the compound taking the benzospiroanthracene as a core.
A display element comprising the organic electroluminescent device.
The invention also relates to an application of the compound taking the benzospiroanthracene as a core, which is applied to the preparation of an organic electroluminescent device,
compared with the prior art, the invention has the beneficial technical effects that:
(1) The compound takes the benzospiroanthracene as a core, is connected to an electron group, has higher hole mobility, and can be used as a material of a hole transport layer of an OLED luminescent device, so that the recombination efficiency of excitons in the luminescent layer can be improved, the energy utilization rate can be improved, and the luminescent efficiency of the device can be improved.
(2) The compound of the invention ensures that the distribution of electrons and holes in the light-emitting layer is more balanced, and improves the hole injection and transmission performance under the proper HOMO energy level; under the proper LUMO energy level, the electron blocking function is also realized, and the recombination efficiency of excitons in the light-emitting layer is improved; the exciton utilization rate can be effectively improved, the device voltage can be reduced, and the current efficiency and the service life of the device can be improved. The compound provided by the invention has good application effect in OLED luminescent devices and has good industrialization prospect.
(3) The compounds of the present application have higher Tg temperatures and lower intermolecular forces. The application of the compound has smaller vapor deposition temperature due to smaller intermolecular force, so that the vapor deposition material is not decomposed for a long time in mass production of the material, and the deformation influence of heat radiation due to the vapor deposition temperature on the Mask is reduced.
Drawings
FIG. 1 is a schematic diagram of the structure of an OLED device using the materials of 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 below with reference to the drawings and examples.
All reactants in the examples described below were purchased from plummet Mo Run, fine chemicals Co., ltd.
Example 1 synthesis of compound 1:
will be 0.01mol of reactant A-1 and 0.012mol of reactant B-1 are dissolved in 150mL of toluene, 0.015mol of potassium tert-butoxide is added, the reaction is carried out for 24 hours at 120 ℃ under the atmosphere of nitrogen, a spot plate is sampled, after the reaction is completed, the mixture is cooled and filtered, the filtrate is distilled off to remove the solvent, the crude product passes through a silica gel column, and the compound 1 is obtained, the yield is 76.85 percent, and the HPLC purity is 99.65 percent; elemental analysis structure (C) 47 H 27 NO) theoretical value: c,90.80; h,4.38; n,2.25; test value: c,90.81; h,4.37; n,2.27.HRMS (EI): theoretical 621.2093 and measured 621.2033.
Synthesis of Compound 223 from example 15:
0.01mol of reactant A-4 and 0.012mol of reactant B-7 were dissolved in 150mL of a toluene/ethanol (V toluene: V ethanol=5:1) mixed solution, and 0.0002mol of Pd (PPh) was added after oxygen removal 3 ) 4 And 0.02mol K 2 CO 3 Reacting at 110 ℃ for 24 hours under the atmosphere of nitrogen, sampling a spot plate, cooling and filtering after the reactant is completely reacted, removing the solvent by rotary evaporation of filtrate, and passing the crude product through a silica gel column to obtain a compound 223, wherein the yield is 76.5 percent and the HPLC purity is 97.36 percent; elemental analysis structure (C) 59 H 36 N 2 ) Theoretical value: c,91.68; h,4.69; n,3.62; test value: c,91.68; h,4.68; n,3.63.HRMS (EI): theoretical value: 772.2878, found: 772.2856.
the synthesis of compound A-1 in example 1 is as follows:
dissolving 0.02mol of raw material C-1 by 60mL of dry THF, preserving heat for 30min at minus 78 ℃, adding 24mL of 1.2M n-butyllithium solution under nitrogen atmosphere, stirring for 1 to 2 hours, continuously adding 0.02mol of raw material D-1 under nitrogen atmosphere, stirring uniformly, slowly heating to room temperature, continuously stirring at room temperature for reacting for 10 to 24 hours, adding 20mL of water into a reaction system, continuously stirring for 1 to 2 hours, separating out a product from the reaction system, filtering, and obtaining 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 10 hours, naturally cooling to room temperature, separating out a product, filtering, washing with water and methanol to obtain a reactant A-1, wherein the HPLC purity is 99.29%, and the yield is 75.5%; HRMS (EI) (high resolution mass spectrometry): theoretical value 444.0514, measured value 444.0528
The following compounds were synthesized by repeating the preparation procedure of example 1 or example 15; wherein reaction condition I indicates that the preparation process is the same as in example 1; reaction condition II indicates that the preparation procedure is the same as in example 15; except that reactants a and B listed in table 1-1 below were used; in Table 1-1, reactant A was synthesized in the same manner as reactant A-1, except that different starting materials C and D were used.
TABLE 1-1
/>
/>
/>
The nuclear magnetic data are shown in tables 1-2 below
/>
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 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 were tested for T1 energy level, thermal performance, HOMO energy level and mobility, respectively, and the test results are shown in table 2.
TABLE 2
| Compounds of formula (I) | T1(eV) | Tg(℃) | Td(℃) | HOMO 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 that: triplet energy level T1 is tested by a fluorescent-3 series fluorescence spectrometer of Horiba, and the test condition of the material is 2 x 10 -5 A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, german fast Co., DSC204F1 differential scanning calorimeter) at a heating rate of 10 ℃/min; the thermal weight loss temperature Td is a temperature at which the weight loss is 1% in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, the nitrogen flow rate is 20mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy measurement system (IPS-3) and was tested as an atmospheric environment. Hole mobility: the material was fabricated as a single charge device and measured by 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.
The effect of the compounds synthesized according to the present invention as hole transport and/or electron blocking materials in devices will be described in detail below with reference to device examples 1 to 26 and device comparative example 1. Device examples 2-26 and device comparative example 1 were identical in fabrication process and the same substrate material and electrode material were used, the film thickness of the electrode material was also consistent, except that the hole transport layer or electron blocking layer material in the device was changed, as compared to device example 1. 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 was washed with an ITO anode layer 2 (film thickness 150 nm), that is, alkali washing, pure water washing, drying, and ultraviolet-ozone washing in this order, to remove organic residues on the transparent ITO surface. On the ITO anode layer 2 after the above washing, HT-1 and P-1 having film thicknesses of 10nm were vapor deposited as hole injection layers 3 by a vacuum vapor deposition apparatus, and the mass ratio of HT-1 to P-1 was 98:2. Then, a 55nm thick compound 13 was evaporated as a hole transport layer 4. Subsequently EB-1 was evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is completed, a light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the light emitting layer comprises BH used by the OLED light emitting layer 6 as a main material, BD as a doping material, the doping proportion of the doping material is 3% by weight, and the film thickness of the light emitting layer is 20nm. After the light-emitting layer 6, vacuum evaporation is continued to be carried out, wherein the mass ratio of ET-1 to Liq is 1:1, the film thickness is 35nm, and the layer is a hole blocking/electron transport layer 7. On the hole blocking/electron transporting layer 7, an Yb layer having a film thickness of 1nm, which is an electron injecting layer 8, was formed by a vacuum vapor deposition apparatus. On the electron injection layer 8, mg having a film thickness of 80nm was produced by a vacuum vapor deposition apparatus: the mass ratio of Mg to Ag in the Ag electrode layer is 1:9, and the Ag electrode layer is a cathode layer 9.
After completing the OLED light emitting device as described above, the anode and cathode were connected by a well-known driving circuit, and the current efficiency of the device, 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 test results of the current efficiency, color and LT95 lifetime at 1000nits luminance of the obtained device are shown in table 4. The molecular structural formula of the related material is shown as follows:
TABLE 3 Table 3
/>
/>
The efficiency and lifetime data for each device example and device comparative example 1 are shown in table 4.
TABLE 4 Table 4
/>
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 of OLED devices of known materials.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A compound taking benzospiroanthracene as a core is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), the dotted line indicates that two groups are connected or not connected;
R 1 、R 2 each independently represents a hydrogen atom;
R 3 、R 4 the structure is represented by a general formula (2) or a general formula (3);
wherein m, n are 0, p, q are 0 or 1, respectively, and m+n+p+q=1;
in the general formula (2) and the general formula (3), R 5 、R 6 Each independently represented by a structure shown in a general formula (4);
L 1 、L 2 each independently represents a single bond;
x in the general formula (3) is represented by-N (R) 9 )-；
X in the general formula (4) 1 、X 2 Are each independently represented by a single bond, -O-, -S-, -C (R 10 )(R 11 ) -or-N (R) 12 ) -; and X is 1 、X 2 Not simultaneously denoted as single bond;
the R is 9 、R 12 Each independently represents phenyl;
the R is 10 、R 11 Each independently represents methyl;
the two adjacent positions marked by the general formula (4) are connected with the two adjacent positions marked by the general formula (2) or the general formula (3) in a parallel ring mode.
2. The benzospiroanthracene-based compound according to claim 1, wherein said R 4 Represented by a hydrogen atom, R 3 The structure is represented by a general formula (2) or a general formula (3).
3. The benzospiroanthracene-based compound according to claim 1, wherein the general formula (1) is any one of the following specific compounds:
。
4. an organic electroluminescent device having a plurality of organic thin film layers between an anode and a cathode, characterized in that at least one organic thin film layer contains the compound of any one of claims 1 to 3 having benzospiroanthracene as a core.
5. The organic electroluminescent device according to claim 4, wherein the multi-layered 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 3.
6. A display element comprising the organic electroluminescent device according to any one of claims 4 to 5.
7. Use of a compound with a benzospiroanthracene core as claimed in any one of claims 1 to 3 for the preparation of an organic electroluminescent device.
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 CN112480133A (en) | 2021-03-12 |
| CN112480133B true 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) |
Families Citing this family (1)
| 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)
| 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 |
-
2019
- 2019-09-11 CN CN201910860880.2A patent/CN112480133B/en active Active
Patent Citations (7)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112480133A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107021926B (en) | Compound containing azaspirofluorene and nitrogen-containing six-membered heterocycle and application of compound in OLED | |
| CN110577510B (en) | Compound based on bis-dimethyl fluorene substituted aniline and organic electroluminescent device prepared from compound | |
| CN109928886B (en) | Compound containing triarylamine and fluorene and application thereof | |
| CN111943941B (en) | Compound with xanthone as core and application thereof | |
| CN110551135A (en) | Compound containing aza five-membered fused ring and application thereof in organic electroluminescent device | |
| CN110885334A (en) | Organic compound with benzo [1,2-b:3, 4-b' ] dibenzofuran as core and application thereof | |
| CN111662187A (en) | Amino-containing organic compound and application thereof | |
| CN111662190A (en) | Organic compound containing pyrene or aza-pyrene and application thereof | |
| CN113004259B (en) | Compound with anthrone skeleton as core and application thereof | |
| CN112479978B (en) | Organic compound with carbazole derivative as core and application thereof | |
| CN110963904A (en) | Compound with ketone and fluorene as cores, preparation method and application thereof | |
| CN109574908B (en) | Compound containing spirodimethyl anthracene fluorene and application thereof in organic electroluminescent device | |
| CN110885333A (en) | Compound with benzo [1,2-b:5,4-b' ] dibenzofuran as core and application thereof | |
| CN110655486A (en) | Compound with dibenzosuberene as core and application thereof | |
| CN112479904B (en) | Organic compound with indeno-anthracene derivative as core and application thereof | |
| CN113072568B (en) | Organic electroluminescent material containing diboron and application thereof | |
| CN112479901B (en) | Organic compound with indeno-anthracene derivative as core and application thereof | |
| CN110003019B (en) | High-mobility organic compound with mesitylene as core and application thereof | |
| CN112480133B (en) | Compound with benzospiroanthracene as core and application thereof | |
| CN109912592B (en) | Compound containing pyridoindole and application of compound in organic electroluminescent device | |
| CN111253410A (en) | Compound with fluorene as core and application thereof | |
| CN111362955A (en) | Organic compound and application thereof to OLED device | |
| CN111362959A (en) | Compound with olefinic bond-containing fluorene as core and application thereof | |
| CN111233844A (en) | Organic compound with carbazole as core, preparation method and application thereof | |
| CN112480092B (en) | Compound with diphenylacridine as core and application thereof in organic electroluminescent device |
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 |
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. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |