CN113121515B - Compound with dibenzo five-membered heterocycle as core and application thereof - Google Patents
Compound with dibenzo five-membered heterocycle as core and application thereof Download PDFInfo
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- CN113121515B CN113121515B CN202010903417.4A CN202010903417A CN113121515B CN 113121515 B CN113121515 B CN 113121515B CN 202010903417 A CN202010903417 A CN 202010903417A CN 113121515 B CN113121515 B CN 113121515B
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- H10K85/649—Aromatic compounds comprising a hetero atom
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- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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Abstract
The invention discloses a compound taking dibenzo five-membered heterocycle as a core and application thereof, belonging to the technical field of semiconductors. The structure of the compound provided by the invention is shown as a general formula (1):the compound contains a dibenzo five-membered heterocyclic parent nucleus structure, has proper HOMO and LUMO energy levels, and has higher Eg and triplet energy level (T1). The compound provided by the invention also has higher glass transition temperature and molecular heat stability; when the material is used as a luminescent layer or a hole blocking or electron transporting layer material of an OLED luminescent device, the three-dimensional property of the structure can be effectively improved by matching with the branched chain in the range of the invention; the whole steric hindrance of the molecule is large, the molecule is not easy to rotate, and the chemical stability of the material is improved. Therefore, after the compound is applied to an OLED device, the luminous efficiency and the service life of the device can be effectively improved.
Description
Technical Field
The invention relates to a compound taking dibenzo five-membered heterocycle as a core and application thereof, belonging to the technical field of semiconductors.
Background
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 OLED devices are further improved. Current research into improving performance of OLED light emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, prolonging the service life of the device, 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 OLED functional material with higher performance is created.
The OLED photoelectric functional materials applied to OLED devices can be divided into two main categories in terms of application, namely charge injection transport materials and luminescent materials. Further, the charge injection transport material may be further classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be further classified into a host light emitting material and a doping material.
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, 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, 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, that is to say, 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 type and the collocation 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 be completely different.
Therefore, according to the current industrial application requirements of the OLED device and the requirements of different functional film layers of the OLED device, the photoelectric characteristic requirements of the device are required to select more suitable OLED functional materials or material combinations with higher performance so as 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
One of the objects of the present invention is to provide a compound having a dibenzofive-membered heterocycle as a core. The compound contains dibenzo five-membered heterocyclic parent nucleus and xanthone branched chain structure, has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and high carrier mobility, and can effectively improve the photoelectric property of an OLED device and prolong the service life of the OLED device through device structure optimization.
A compound with dibenzo five-membered heterocycle as a core has a structure shown in a general formula (1):
in the general formula (1), X represents-O-or-S-;
xa is represented by-O-, -S-, -C (Ra) (Rb) -or-N (Rc), ra, rb, rc are each independently represented as C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
l is identical or different and is represented by a single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
Z 1 represented by a nitrogen atom or C (R), adjacent R may be bonded to form a ring,Z 1 the same or different for each occurrence;
Z 2 represented by nitrogen atom or C (R) 0 ) Adjacent R 0 Can be bonded to form a ring, Z 2 The same or different for each occurrence;
Z 3 、Z 4 、Z 5 、Z 6 represented by nitrogen atom or C (R) 1 )，R 1 Each occurrence of the same or different, adjacent R 1 Can be bonded to form a ring;
Z 7 represented by nitrogen atom or C (R) 2 ) Adjacent R 2 Can be bonded to form a ring, Z 7 The same or different for each occurrence;
r is the same or different and is represented by hydrogen atom, protium atom, deuterium atom, tritium atom, halogen atom, cyano group, C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, a structure represented by the general formula (2) or the general formula (3);
R 0 、R 1 、R 2 each occurrence of which is the same or different and is represented by a hydrogen atom, protium atom, deuterium atom, tritium atom, halogen atom, cyano group, C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, a structure shown in a general formula (2), a general formula (3) or a general formula (4);
when R is 2 Represented by the general formula (2) or the general formula (3), L is only Z 3 Or Z is 6 Bonding each other;
in the general formula (1), at least one R is represented by the general formula (2) or the general formula (3), or 0 、R 1 And R is 2 At least one of the structures represented by the general formula (2), the general formula (3) or the general formula (4) exists;
in the general formula (4), X 1 Represented by-O-or-S-;
in the general formula (2), the general formula (3) and the general formula (4), Z 8 Represented by nitrogen atom or C (R) 4 ) Adjacent R 4 Can be bonded to form a ring, Z 8 The same or different at each occurrenceSimultaneously; l (L) 1 、L 2 And L 3 Represented independently as single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
R 3 represented as substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
R 4 represented by hydrogen, protium, deuterium, tritium, halogen, cyano, C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
the substituents of the "substituted or unsubstituted" above groups are optionally selected from: cyano, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-30 Aryl, C 2-30 One or more of the heteroaryl groups of (a);
the hetero atom in the heteroaryl and the heteroarylene is selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the present invention, the general formula (2) is represented by any one of the following structures:
as a further improvement of the present invention, the general formula (3) is represented by any one of the following structures:
R 3 represented by methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, adamantyl, substituted or unsubstituted phenyl, substitutedOr one of unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted azacarbazolyl;
as a further improvement of the present invention, the general formula (4) is represented by the following structure:
X 1 represented as-O-or-S-.
As a further improvement of the present invention, the structure of the compound is represented by the general formulae (II-1) to (II-11):
the symbols in the formulae (II-1) to (II-11) have the meanings defined above.
As a further improvement of the present invention, Z in the general formulae (II-1) to (II-11) 1 Represented by C (R), Z 2 Represented by C (R) 0 )，Z 3 、Z 4 、Z 5 、Z 6 Represented by C (R) 1 )，Z 7 Represented by C (R) 2 )，Z 8 Represented by C (R) 4 ) R, R of said 0 、R 1 、R 2 、R 4 Represented by hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, adamantyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthaleneA pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dimethylfluorenyl group, or a substituted or unsubstituted diphenylfluorenyl group.
As a further improvement of the present invention, Z in the general formulae (II-1) to (II-11) 1 Represented by C (R), Z 2 Represented by C (R) 0 )，Z 3 、Z 4 、Z 5 、Z 6 Represented by C (R) 1 )，Z 7 Represented by C (R) 2 )，Z 8 Represented by C (R) 4 ) R, R of said 0 、R 1 、R 2 Represented by hydrogen atom, R 4 Represented by a hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, adamantyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted dimethylfluorenyl group or substituted or unsubstituted diphenylfluorenyl group, and at least one R 4 Not indicated as hydrogen atoms.
As a further improvement of the present invention, in the general formulae (II-1) to (II-11), X represents-O-or-S-;
xa is represented by-O-, -S-, -C (Ra) (Rb) -or-N (Rc), ra, rb, rc are each independently represented as C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
l is identical or different and is represented by a single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
Z 1 represented by nitrogen atoms or C (R), Z 1 The same or different for each occurrence;
Z 2 represented by nitrogen atom or C (R) 0 )，Z 2 The same or different for each occurrence;
Z 3 、Z 4 、Z 5 、Z 6 represented by nitrogen atom or C (R) 1 )，R 1 The same or different for each occurrence;
Z 7 represented by nitrogen atom or C (R) 2 )，Z 7 The same or different for each occurrence;
R、R 0 、R 1 、R 2 each occurrence of which is the same or different and is represented by a hydrogen atom, protium atom, deuterium atom, tritium atom, halogen atom, cyano group, C 1-10 Alkyl, substituted or unsubstituted C 6-30 An aryl group;
X 1 represented by-O-or-S-;
Z 8 represented by nitrogen atom or C (R) 4 )，Z 8 The same or different for each occurrence;
L 1 、L 2 and L 3 Represented independently as single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted 5 to 30 membered heteroarylene containing one or more heteroatoms;
R 3 represented as substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
R 4 represented by hydrogen, protium, deuterium, tritium, halogen, cyano, C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 2-30 Heteroaryl of (a);
the substituents of the "substituted or unsubstituted" above groups are optionally selected from: cyano, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-30 Aryl, C 2-30 One or more of the heteroaryl groups of (a);
the hetero atom in the heteroaryl and the heteroarylene is selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, the L, L 1 、L 2 And L 3 Each independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstitutedAn anthrylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted naphthyridine group;
r is hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, adamantyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted dimethylfluorenyl group, substituted or unsubstituted diphenylfluorenyl group, structure shown in the general formula (2) or the general formula (3);
the R is 0 、R 1 、R 2 Each occurrence of the same or different structure represented by a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, an adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a structure represented by the general formula (2), the general formula (3) or the general formula (4);
said Ra, rb, rc, R 3 Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl,One of substituted or unsubstituted azacarbazolyl groups;
the R is 4 Represented by one of a hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, adamantyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted dimethylfluorenyl group, substituted or unsubstituted diphenylfluorenyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted azacarbazolyl group;
the substituent of the above group "substituted or unsubstituted" is optionally one or more selected from methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, adamantyl, phenyl, naphthyl, naphthyridinyl, biphenyl, terphenyl, furyl, dibenzofuranyl, carbazolyl or pyridyl.
As a further improvement of the invention, adjacent R 0 Adjacent R 1 Adjacent R 2 Adjacent R 4 Can be bonded to form a benzene ring.
As a further improvement of the invention, the specific structure of the compound is:
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Another object of the present invention is to provide an organic electroluminescent device. When the compound is applied to an OLED device, the stability of a film layer can be kept high through the structural optimization of the device, the photoelectric property of the OLED device and the service life of the OLED device can be effectively improved, and the compound has good application effect and industrialization prospect.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device comprises an anode, a cathode and an organic functional layer, wherein the organic functional layer is positioned between the anode and the cathode, and the organic functional layer contains the compound taking dibenzofive-membered heterocycle as a core.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the organic functional layer comprises a light-emitting layer and/or a hole blocking and/or electron transporting layer, and the light-emitting layer and/or the hole blocking and/or electron transporting layer contains the compound taking the dibenzofive-membered heterocycle as a core.
It is a further object of the present invention to provide an illumination or display element. The organic electroluminescent device can be applied to lighting or display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are improved greatly; meanwhile, the service life of the OLED light-emitting device is obviously prolonged, and the OLED light-emitting device has a good application effect and good industrialization prospect.
The technical scheme for solving the technical problems is as follows: an illumination or display element comprising the organic electroluminescent device described above.
The beneficial effects of the invention are as follows:
the pi conjugated effect in the compound of the invention enables the compound to have strong electron transmission capability, and the high electron transmission rate can reduce the initial voltage of the device and improve the efficiency of the organic electroluminescent device.
The compound of the invention takes dibenzo five-membered heterocycle as a core and is connected with xanthone branched chains, the structural rigidity is strong, the steric hindrance is large, and the compound is not easy to rotate, so that the three-dimensional structure of the compound material of the invention is more stable; the introduction of different branched chains on the dibenzo five-membered heterocyclic parent nucleus increases the asymmetry of the molecule and can reduce the crystallinity of the molecule; intermolecular packing tends to increase the probability of exciton-exciton annihilation, resulting in low device efficiency, significant efficiency roll-off, and particularly significant lifetime degradation; when R is 2 Represented by the general formula (2) or the general formula (3), L and Z 3 Or Z is 6 The mutual bonding can further effectively increase the steric hindrance of molecules, inhibit the accumulation among the molecules, reduce the probability of exciton-exciton annihilation, improve the efficiency of the device, reduce the efficiency roll-off, and particularly obviously prolong the service life of the device;
the compound provided by the invention has deeper HOMO and LUMO energy levels and high electron mobility, and the HOMO and LUMO energy levels can be freely adjusted within a certain range through modification of other aromatic groups; the higher energy level of T1 ensures the energy transfer efficiency between the host and the guest, and can inhibit the energy loss in the luminescent layer when being used as a hole blocking layer material, so that the material can be used as an electronic luminescent main body material and also can be used as a hole blocking layer material and an electron transport layer material;
when the compound is used as a hole blocking and electron transporting layer of an OLED, the proper LUMO energy level and high electron mobility can effectively realize electron injection and accelerate electron transport, so that the recombination efficiency of excitons in a light emitting layer is improved, the energy loss is reduced, and the light emitting efficiency of the material after being applied to a device is improved.
When the compound is used as a main material of a luminescent layer, proper LUMO energy level and high electron mobility improve the injection and transmission performance of electrons, and the compound is matched with a hole type main material for use, so that the distribution of electrons and holes in the luminescent layer is more balanced, the exciton utilization rate can be effectively improved, the efficiency roll-off under high current density is reduced, the device voltage is reduced, and the current efficiency and the service life of the device are improved.
The compound is designed on the dibenzo five-membered heterocyclic parent nucleus, after the substituent groups are added, the intermolecular distance is increased, the interaction force between the intermolecular cores is weakened, the Tg temperature of the material is increased, active C-H bonds are passivated, and the stability of the material is improved; the addition of the substituent groups increases the molecular weight of the material, but in the practical application process, the evaporation temperature of the material is still lower, the temperature interval between the processing temperature and the decomposition temperature of the material is widened, and the use processing window of the material is improved.
The compound has the characteristics of high rigidity, difficult crystallization, difficult aggregation among molecules, good film forming property and high glass transition temperature and thermal stability, so that the compound can keep the stability of a film layer formed by a material and prolong the service life of an OLED device when being applied to the OLED device. After the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the OLED light-emitting device is obviously prolonged, and the OLED light-emitting device has a good application effect and good industrialization prospect.
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 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 a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
All materials in the examples below were purchased from the tobacco stand Mo Run fine chemical Co., ltd.
Example 1 synthesis of compound 1:
0.01mol of intermediate D-1 was added with 0.012mol of starting material E-1 to 120mL of toluene: to a mixed solvent of ethanol=2:1, 0.02mol of potassium carbonate was added, and after deoxidization, 0.0002mol of Pd (PPh 3 ) 4 Reacting at 110 ℃ for 48 hours in a nitrogen atmosphere, sampling a spot plate, cooling and filtering after the reactant is reacted completely, removing the solvent by rotary evaporation of filtrate, and passing the crude product through a silica gel column to obtain a compound 3;
the procedure of example 1 was repeated to synthesize the following target compounds; the reaction conditions were the same except that intermediate D and starting material E listed in table 1 below were used;
TABLE 1
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Wherein the synthetic route of intermediates D-1 and D-3 is as follows:
intermediate D-1 (1) in a 250ml three-port bottle, under the protection of nitrogen, 0.01mol of raw material A-1,0.01 mol of raw material B-1 and 150ml of toluene are added, stirred and mixed, and then 5X 10-5mol of Pd is added 2 (dba) 3 ，5×10-5mol P(t-Bu) 3 Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, sampling a dot plate, and displaying no bromide to remain, wherein the reaction is complete; naturally cooling to room temperature, filtering, steaming the filtrate until no fraction exists, and passing through a neutral silica gel column to obtain intermediate C-1 with HPLC purity of 96.87% and yield of 78.49%.
0.1mol of the intermediate C-1 obtained and 0.15mol of a boric acid ester of bis-pinacolato were added to 100mL of 1, 4-dioxane, and after deoxygenation, 0.002mol of Pd (dba) was added 2 And 0.004mol of Xphos (2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl) are reacted for 20 hours at 110 ℃ in the atmosphere of nitrogen, a spot plate is sampled, after the reaction of reactants is completed, the mixture is cooled and filtered, the filtrate is distilled off to remove the solvent, and the crude product is passed through a silica gel column to obtain an intermediate D-1.
Repeating the preparation process of the intermediate D-1 to synthesize a target intermediate D-2; the reaction conditions were the same except that starting material a, starting material B and intermediate C, listed in table 2 below, were used.
Intermediate D-3 (1) 0.1mol of feed A-1 and 0.12mol of feed B-3 were added to 100mL of toluene: to a mixed solvent of ethanol=2:1, 0.02mol of potassium carbonate was added, and after deoxidization, 0.0002mol of Pd (PPh 3 ) 4 Reacting at 110 ℃ for 24 hours in nitrogen atmosphere, sampling a spot plate, cooling and filtering after the reactant is reacted completely, removing the solvent by rotary evaporation of filtrate, and passing the crude product through a silica gel column to obtain an intermediate C-3;
(2) 0.1mol of the intermediate C-1 obtained and 0.15mol of the bis-pinacolato borate were added to 100mL of 1, 4-oIn dioxane, 0.002mol Pd (dba) is added after deoxidization 2 And 0.004mol of Xphos (2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl) are reacted for 24 hours at 110 ℃ under the atmosphere of nitrogen, a spot plate is sampled, after the reaction of reactants is completed, the mixture is cooled and filtered, the filtrate is distilled off to remove the solvent, and the crude product is passed through a silica gel column to obtain an intermediate D-3. Repeating the preparation process of the intermediate D-3 to synthesize target compounds D-4 to D-12; the reaction conditions were the same except that starting material a, starting material B and intermediate C, listed in table 2 below, were used.
TABLE 2
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The data of the nuclear magnetic resonance hydrogen spectrum of the compounds of the above examples in the present invention are shown in Table 3-1:
TABLE 3-1
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The following reaction types involved in the preparation of compound 13, compound 14, compound 326, compound 345, compound 398, compound 413, compound 428, compound 423, compound 460, compound 461, compound 124, compound 107, compound 273, compound 365, compound 5, compound 522, compound 538, compound 576 and compound 582 are referred to the above preparation examples, and the nuclear magnetic resonance hydrogen spectra and part of the elemental analysis and mass spectrum data of these compounds are shown in tables 3 to 2:
TABLE 3-2
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The compound provided by the invention is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and is suitable for HOMO and LUMO energy levels, and can be used as a light-emitting layer and a hole blocking/electron transport layer material. The compounds prepared in the above examples of the present invention were subjected to thermal performance, T1 energy level and HOMO energy level tests, respectively, and the results are shown in table 4.
TABLE 4 Table 4
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Note that: the triplet state energy level T1 is tested by a Hitachi F4600 fluorescence spectrometer, 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 highest occupied molecular orbital HOMO energy level was tested by the ionization energy measurement system (IPS-3), tested as an atmospheric environment; the lowest unoccupied molecular orbital LUMO level is obtained by subtracting Eg from the HOMO level, which is calculated from the tangent at the maximum absorption wavelength of the uv absorption curve of the single film.
As shown in the data of the table, the compound has high glass transition temperature, can improve the phase stability of a material film, and further improves the service life of a device; the compound contains a strong electron acceptor and is matched with a hole type main body material, so that electrons and holes of an OLED device applying the compound reach an equilibrium state, the recombination rate of the electrons and the holes is ensured, the efficiency and the service life of the OLED device are improved, the material has a high triplet state energy level, and the energy loss of a luminescent layer can be blocked, so that the luminous efficiency of the device is improved. Meanwhile, the material has proper HOMO and LUMO energy levels, so that the problem of carrier injection can be solved, and the device voltage can be reduced; therefore, after the organic material is applied to different functional layers of the OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
The effect of the compounds of the present invention in the application of OLED devices will be described below by way of device examples. Device examples 2-46 and device comparative examples 1-6 were identical in fabrication process and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept uniform, except that the light-emitting layer or hole blocking or electron transporting layer material was changed in the devices, the composition of each layer of each device was as shown in table 5, and the performance test results of each device were as shown in tables 6 and 7.
Device example 1
As shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness 150 nm) is washed, that is, washed with a cleaning agent (semiconductor M-L20), washed with pure water, dried, and then washed with ultraviolet-ozone 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 97:3. Next, HT-1 was evaporated to a thickness of 60nm as the hole transport layer 4. Subsequently EB-1 was evaporated to a thickness of 40nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, a luminescent layer 6 of the OLED luminescent device is manufactured, the structure of the luminescent layer comprises the compound 3 and GH-2 used by the OLED luminescent layer 6 as main materials, GD-1 as doping materials, the mass ratio of the compound 3 to the GH-2 to the GD-1 is 47:47:6, and the thickness of the luminescent layer is 40nm. After the light-emitting layer 6 was deposited, vacuum deposition of HB-1 was continued to give a film thickness of 5nm, and this layer was a hole blocking layer 7. After the luminescent layer 7, vacuum evaporation of ET-1 and Liq is continued, the mass ratio of ET-1 to Liq is 1:1, the film thickness is 35nm, and the layer is an electron transport layer 8. On the electron transport layer 8, a Yb layer having a film thickness of 1nm was formed by a vacuum vapor deposition apparatus, and this layer was an electron injection layer 9. On the electron injection layer 9, 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 used as the cathode layer 10. The molecular structural formula of the related material is shown as follows:
TABLE 5
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TABLE 6
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As can be seen from the results of table 6, the dibenzo five-membered heterocycle based compound prepared in the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the device of comparative example 1, the use of the dibenzo five-membered heterocycle based compound as a light emitting layer or a hole blocking layer or an electron transport layer has a significantly improved efficiency and lifetime compared with the known OLED materials, in particular, the lifetime of the device is significantly improved, and the use of the dibenzo five-membered heterocycle based compound as a hole blocking layer or an electron transport layer has an effect of reducing the voltage of the device. The use of the compounds of the present invention as green phosphorescent hosts significantly improves device efficiency, and in particular device lifetime, as compared to device examples 21, 22 and device comparative examples 2-6;
to compare the efficiency decay of different devices at high current densities, the efficiency decay coefficients of the devices are defined Indicating a drive current of 100mA/cm 2 Ratio between maximum efficiency of device mu 100 and maximum efficiency of device mu m and maximum efficiency,/DEG>The larger the value, the more serious the efficiency roll-off of the device is, and on the contrary, the problem of rapid roll-off of the device under high current density is controlled. The present invention examined device examples 1-46, device comparative examples 1-6 for the efficiency decay factor +.>The results are shown in Table 7:
TABLE 7
As can be seen from the data in table 7, the organic light emitting devices prepared by using the compounds of the present invention have smaller efficiency attenuation coefficients compared with comparative examples 1 to 6, and particularly have a remarkable effect of reducing the efficiency roll-off compared with comparative examples 2 and 3, which indicates that the organic electroluminescent devices prepared by using the compounds of the present invention can effectively reduce the efficiency roll-off, and have unexpected technical effects.
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 (5)
1. A compound taking dibenzo five-membered heterocycle as a core is characterized in that the specific structure of the compound is as follows:
any one of them.
2. An organic electroluminescent device comprising an anode, a cathode and an organic functional layer, wherein the organic functional layer is located between the anode and the cathode, and the organic electroluminescent device is characterized in that at least one organic functional layer of the organic electroluminescent device contains the dibenzo five-membered heterocycle-based compound according to claim 1.
3. The organic electroluminescent device according to claim 2, wherein the organic functional layer comprises a light-emitting layer, wherein the light-emitting layer contains the dibenzofive-membered heterocycle-based compound according to claim 1.
4. The organic electroluminescent device according to claim 2, wherein the organic functional layer comprises a hole blocking layer or an electron transporting layer, wherein the hole blocking layer or the electron transporting layer contains the dibenzofive-membered heterocycle-based compound according to claim 1.
5. A lighting or display element, characterized in that it comprises an organic electroluminescent device as claimed in any one of claims 2 to 4.
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| CN113896715B (en) * | 2021-10-14 | 2023-07-04 | 大连理工大学 | Acridone organic electroluminescent material and application thereof |
| WO2024186104A1 (en) * | 2023-03-06 | 2024-09-12 | 주식회사 엘지화학 | Compound and organic light-emitting device comprising same |
| CN116063293B (en) * | 2023-04-06 | 2023-07-28 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device |
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