CN116283909B - Organic electronic transmission material and preparation method and application thereof - Google Patents

Organic electronic transmission material and preparation method and application thereof Download PDF

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CN116283909B
CN116283909B CN202310547015.9A CN202310547015A CN116283909B CN 116283909 B CN116283909 B CN 116283909B CN 202310547015 A CN202310547015 A CN 202310547015A CN 116283909 B CN116283909 B CN 116283909B
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CN116283909A (en
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汪康
李贺
徐佳楠
王士凯
韩瑞锋
段晓伟
张思铭
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Jilin Optical and Electronic Materials Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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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Abstract

The invention provides an organic electronic transmission material, a preparation method and application thereof, and a structural general formula is shown in the specification. The organic electron transport material provided by the invention has sp at 9 positions of fluorene ring 3 The hybridized carbon maintains the spatial configuration of the compound; the bridged substituted heteroaryl enables the compound to have electron-withdrawing property, is favorable for electron transmission, enhances the recombination of electrons and holes in the light-emitting layer, and thus improves the light-emitting efficiency of the device; substitution of heteroaryl at different positions of phenyl or naphthyl further avoids the occurrence of large planes in the molecule to enhance intermolecular interactions, resulting in shortened device lifetime; meanwhile, the heteroaryl groups are bridged at different positions of the 9-position benzene ring of fluorene, so that the reduction of electron transmission caused by bipolar molecular property can be avoided. In particular, the present invention has developed an electron transport material having high mobility, so that the OLED prepared therefrom has the performance advantages of high luminous efficiency and long life.

Description

Organic electronic transmission material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic electronic transmission material and a preparation method and application thereof.
Background
Compared with the traditional display and illumination technology, the organic light-emitting diode (OLED) has obvious advantages such as no need of a backlight source, light weight, low energy consumption, high response speed, flexibility, clearness in displaying moving images, no smear and the like, and can meet the performance requirements of people on an information display system in multiple aspects.
The OLED specifically includes electrode material layers and organic functional materials sandwiched between different electrode layers, including a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). The ETL layer is a key component in the OLED structure and is responsible for adjusting the injection speed and injection quantity of electrons, but the electron mobility of the common organic material is lower, the hole mobility is higher, and the unbalance of electrons and holes in the device is caused, so that the efficiency and the stability of the device are reduced.
In recent years, although research on organic electron transport materials has been conducted more, development of an electron transport material having high mobility so that an OLED prepared therefrom has performance advantages of high luminous efficiency and long life has been a problem that a person skilled in the art is urgently required to solve.
Disclosure of Invention
In view of the above, the present invention provides an organic electron transport material and a method for preparing the same, which are capable of providing an OLED having high luminous efficiency and long life by developing an electron transport material having high mobility.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic electron transport material having a structure represented by formula I:
；
i is a kind of
Wherein,,
Z 1 ~Z 3 independently represent C, N atoms, Z 1 ~Z 3 Wherein the number of N is 2 or 3;
Z 4 ~Z 9 independently represent C, N atoms, Z 4 ~Z 9 Wherein N is an integer of 0 to 3；
R is independently selected from hydrogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C24 aryl, and substituted or unsubstituted C3-C24 heteroaryl;
a is an integer of 1 to 5;
and when Z is 4 ~Z 9 When the two are C atoms, R has at least one strong electron withdrawing group, and is selected from cyano, triazine, triazole, pyridazine, pyrimidine, pyrazine, imidazole, oxazole, thiazole, pyrazole, pyridine, benzimidazole, benzothiazole and quinoline;
R 1 represents a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C6-C24 aryl group, or a substituted or unsubstituted C3-C24 heteroaryl group;
m, n independently represent integers of 0, 1, 2;
Ar 1 ，Ar 2 independently represents a substituted or unsubstituted C6-C24 aryl group, a substituted or unsubstituted C3-C24 heteroaryl group.
Further, R is selected from cyano;
r is selected from substituted or unsubstituted C1-C6 alkyl, preferably methyl, ethyl, n-propyl and isopropyl;
R，Ar 1 ，Ar 2 when selected from substituted or unsubstituted C6-C24 aryl groups, phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, dimethylfluorenyl, benzofluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, naphtonaphthyl, fluoranthenyl, azulenyl, 9-dimethylfluorenyl, phenanthryl, and combinations thereof are preferred;
R，Ar 1 ，Ar 2 when selected from substituted or unsubstituted C3 to C24 heteroaryl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolylBenzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, carbazolyl and benzocarbazolyl.
R 1 When selected from substituted or unsubstituted C1-C3 alkyl, methyl and ethyl are preferred;
R 1 when selected from substituted or unsubstituted C6 to C24 aryl, phenyl, naphthyl and biphenyl are preferred;
R 1 when selected from substituted or unsubstituted C3 to C24 heteroaryl, pyridinyl, pyrazinyl, pyrimidinyl and pyridazinyl are preferred.
Further, Z 1 ~Z 3 Are all N;
r represents cyano, methyl, phenyl, biphenyl, naphthyl, anthracenyl, pyridyl, pyrazinyl, pyrimidinyl, and pyridazinyl;
R 1 represented by methyl, phenyl, biphenyl, naphthyl;
m, n independently represent 0 or 1;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl, dibenzofuranyl, carbazolyl, 9-dimethylfluorenyl, phenanthryl, and combinations thereof.
Further, R represents cyano, methyl, phenyl, pyridinyl;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl;
the general formula I includes the following structure:
。
in the above-mentioned technical scheme, the method comprises the steps of,
the substitution positions are defined as follows:
。
the term "substituted or unsubstituted" refers to the number of carbon atoms of a substituent that make up the unsubstituted number of carbon atoms, regardless of the number of carbon atoms in the substituent.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, chrysene, furanyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, indazolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, or a substituent linked by two or more of the substituents indicated above, or not.
Aryl refers to monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems, polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings being "fused");
heteroaryl groups include monocyclic aromatic groups and polycyclic aromatic ring systems of at least one heteroatom including, but not limited to O, S, N, P, B, si and Se;
the compounds specifically have the following structure, but are not limited thereto:
。
synthetic route
1）N 2 Under the protection, adding reactant 1 (1.0 eq), reactant 2 (1.3-1.5 eq), palladium catalyst (0.01-0.02 eq) and alkali (2.0-2.3 eq) into a mixed solvent of toluene, ethanol and water (2-4:1:1) respectively, heating to 80-100 ℃, reacting for 8-10h, cooling to room temperature, adding water, filtering after solid precipitation is finished, drying a filter cake, purifying the rest substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the intermediate 1.
2）N 2 Under the protection, the intermediate is 1%1.0 eq), reactant 3 (1.0-1.2 eq), palladium catalyst (0.01-0.02 eq) and alkali (2.0-2.3 eq) are respectively added into mixed solvent of toluene, ethanol and water (2-4:1:1), the temperature is raised to 80-100 ℃, the reaction is carried out for 8-12h, the room temperature is cooled, water is added, after the solid precipitation is finished, the filtration is carried out, the filter cake is dried, the residual substances are purified by using a column chromatography, the solvent is removed from the filtrate, and the obtained solid is dried, thus obtaining the formula I.
。
Wherein,,
reactant 1 and reactant 3 can be obtained from known starting materials or synthesized by:
under the protection of nitrogen, the reactant b (1.0 eq), the reactant a (1.5-1.8 eq), the palladium catalyst (0.05-0.1 eq) and the potassium acetate (2.0-3.0 eq) are dissolved in N, N-Dimethylformamide (DMF), the temperature is raised to 85-95 ℃, the reaction is carried out for 8-12h, and a rotary evaporator is used for removing the solvent. Adding dichloromethane into the residue, stirring, filtering, and purifying the residual substances by using column chromatography to obtain a reactant 1;
reactant 3 was synthesized by the method of synthesizing reactant 1, and reactant a was replaced with reactant c.
；
Hal is selected from Cl, br; hal1 is selected from Br, I;
r' isOr->；
A is boric acid or pinacol ester of biboric acid;
R、R 1 、Ar 1 ~Ar 2 、Z 1 ~Z 3 、Z 4 ~Z 9 and m, n have the definitions given above.
Further, the palladium catalyst may be: pd (Pd) 2 (dba) 3 ，Pd(PPh 3 ) 4 ，PdCl 2 ，PdCl 2 (dppf)，Pd(OAc) 2 ，Pd(PPh 3 ) 2 Cl 2 ，NiCl 2 (dppf)；
The base may be: k (K) 2 CO 3 ，K 3 PO 4 ，Na 2 CO 3 ，CsF，Cs 2 CO 3 ，t-BuONa。
In the invention, two halogens exist in the synthesis of the intermediate 1 and the reactant 1, according to the characteristic that the reactivity I > Br > Cl in the palladium catalytic coupling reaction, the reaction site is controlled by controlling the reaction condition to prepare the intermediate, and the by-product is removed by column chromatography or silica gel funnel purification reaction, so as to obtain the target compound. The following are referred to in the common general knowledge:
transition metal organic chemistry (original sixth edition), robert H-Crabtree (Robert H. Crabtree), press: publication time of Shanghai Shandong university Press: 2017-09-00, ISBN:978-7-5628-5111-0, page 388.
Organic chemistry and photoelectric Material Experimental Instructions, chen Runfeng, press: university of east south Press, publication time: 2019-11-00, ISBN:9787564184230, page 174.
The invention also discloses application of the organic electronic transmission material in preparing organic electroluminescent devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an organic electron transport material, wherein one substituent at 9-position of fluorene in the compound is benzene substituted by naphthyl, and the other substituent is R of the invention 1 The radicals shown are, at the same time, the phenyl ring and the naphthyl radical being attached to the heteroaryl radical directly or via phenylene, respectively. The invention provides an electron transport materialThe prepared OLED device has good comprehensive performance, and particularly has obvious improvement effect on the aspects of service life and luminous efficiency of the device.
In the present invention, sp at 9-position of fluorene ring 3 The hybrid carbon can keep the spatial configuration of the compound, and avoid poor film forming property and short service life of the device caused by molecular stacking; the heteroaryl is introduced to enable the compound to have the property of electron attraction, thereby being beneficial to electron transmission and enhancing the recombination of electrons and holes in the luminescent layer, and further improving the luminescent efficiency of the device; bridging heteroaryl groups at different positions of the 9-benzene ring of fluorene can avoid weakening electron transmission caused by bipolar molecules (which are beneficial to hole transmission and electron transmission); simultaneously, the heteroaryl is substituted at different positions of the phenyl or the naphthyl, so that the occurrence of a large plane in a molecule can be further avoided, the interaction between molecules is weakened, and the service life of the device is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of intermediates 1-165 in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 165 in example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound 196 in example 2.
Fig. 4 is a nuclear magnetic resonance hydrogen spectrum of compound 393 of example 3.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of compound 416 in example 4.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: synthesis of Compound 165
；
Under nitrogen, reactant b-165 (20 mmol), reactant a-165 (30 mmol, CAS: 1432909-93-7), pd (PPh 3 ) 4 (1 mmol) and potassium acetate (40 mmol) were dissolved in DMF, warmed to 90℃and reacted for 8h, and the solvent was removed using a rotary evaporator. Adding dichloromethane into the residue, stirring, filtering, and purifying the rest material by column chromatography to obtain reactants 1-165;
N 2 under protection, reactants 1-165 (20 mmol), reactants 2-165 (30 mmol, CAS: 73207-97-3), pd (PPh) 3 ) 4 (0.2 mmol) and K 2 CO 3 (40 mmol) are added into a mixed solvent of toluene, ethanol and water (3:1:1) respectively, the temperature is raised to 85 ℃, the reaction is carried out for 8 hours, the temperature is cooled to room temperature, water is added, after the solid is separated out, the filtration is carried out, a filter cake is dried, the residual substances are purified by a column chromatography, the solvent is removed from the filtrate by a rotary evaporator, and the obtained solid is dried, thus obtaining the intermediate 1-165. (5.00 g, yield: 56%, test value MS (ESI, M/Z): [ M+H ]] + = 445.98, mass spectrometer model Waters XEVO TQD, low precision, test with ESI source);
the nuclear magnetic resonance hydrogen spectra of intermediates 1-165 are shown in FIG. 1:
N 2 under protection, intermediate 1-165 (20 mmol), reactant 3-165 (22 mmol, CAS: 248624-48-7), pd (PPh) 3 ) 4 （0.2mmol）、K 2 CO 3 (40 mmol) respectively adding into mixed solvent of toluene, ethanol and water (3:1:1), heating to 90deg.C, reacting for 10h, cooling to room temperature, adding water, filtering after solid precipitation, oven drying the filter cake, purifying the rest material by column chromatography, removing solvent from the filtrate by rotary evaporator, and drying the obtained solid to obtain the final productObject 165 (11.79 g, yield: 64%, test value MS (ESI, M/Z): [ M+H ]] + = 921.19）；
The nuclear magnetic resonance hydrogen spectrum of compound 165 is shown in fig. 2:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 87.46, H, 4.93, N, 7.61
Test value: c, 87.38, H, 5.02, N, 7.65
Example 2: synthesis of Compound 196
；
Synthesizing a compound 196 according to the method for synthesizing the compound 165, and replacing reactants a-165 and reactants 3-165 with reactants a-196 and reactants 3-196;
the reaction gave compound 196 at 11.05g, yield: 61%, test value MS (ESI, M/Z) [ M+H ]] + = 906.15）；
The nmr hydrogen spectrum of compound 196 is shown in fig. 3:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.91, H, 4.90, N, 6.19
Test value: c, 88.82, H, 4.98, N, 6.23.
Example 3: synthesis of Compound 393
；
Under nitrogen, reactant b-165 (20 mmol), reactant c-393 (25 mmol), pd (PPh) 3 ) 4 (1 mmol) and potassium acetate (40 mmol) were dissolved in DMF, warmed to 90℃and reacted for 8h, and the solvent was removed using a rotary evaporator. Adding dichloromethane into the residue, stirring, filtering, and purifying the residual material by column chromatography to obtain reactant 3-393;
N 2 under protection, reactants 1-393 (20 mmol), reactants 2-393 (22 mmol), pd (PPh) 3 ) 4 （0.2eq）、K 2 CO 3 (40 mmol) respectively adding into a mixed solvent of toluene, ethanol and water (3:1:1), heating to 90 ℃, reacting for 10 hours, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the rest substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate 1-393;
synthesizing a compound 393 according to the method for synthesizing the intermediate 1-393, and respectively replacing reactants 1-393 and reactants 2-393 with reactants 3-393 and the intermediate 1-393;
the reaction gave compound 393 at 9.98g, yield: 63, test value MS (ESI, M/Z) [ M+H ]] + = 792.01）；
The nmr hydrogen spectrum of compound 393 is shown in fig. 4:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.07, H, 4.84, N, 7.08
Test value: c, 87.98, H, 4.93, N, 7.13.
Example 4: synthesis of Compound 416
；
Synthesizing an intermediate 1-416 according to the method for synthesizing the intermediate 1-393, and replacing reactants 1-393 with reactants 1-196;
synthesizing the compound 416 according to the method for synthesizing the intermediate 1-393, and replacing the reactants 1-393 and the reactants 2-393 with the reactants 3-416 and the intermediate 1-416 respectively;
the reaction gave compound 416 as 9.96g, yield: 59, test value MS (ESI, M/Z) [ M+H ]] + = 844.08）；
The nmr hydrogen spectrum of compound 416 is shown in fig. 5:
characterization:
HPLC purity: > 99.8%.
Elemental analysis:
theoretical value: c, 88.33, H, 5.02, N, 6.65
Test value: c, 88.21, H, 5.11, N, 6.71.
Examples 5 to 55
The synthesis of the following compounds, whose molecular formulas and mass spectra are shown in Table 1 below, was accomplished with reference to the synthesis methods of examples 1-4.
Table 1 molecular formula and mass spectrum
Examples Compounds of formula (I) Molecular formula Mass spectrometry test values
Example 5 1 C 62 H 42 N 4 844.08
Example 6 17 C 50 H 34 N 4 691.89
Example 7 23 C 50 H 34 N 4 691.91
Example 8 27 C 56 H 38 N 4 768.00
Example 9 33 C 67 H 44 N 4 906.17
Example 10 56 C 61 H 40 N 4 830.16
Example 11 57 C 55 H 36 N 4 753.97
Example 12 62 C 55 H 36 N 4 753.96
Example 13 64 C 55 H 36 N 4 753.97
Example 14 70 C 50 H 34 N 4 691.90
Example 15 74 C 50 H 34 N 4 691.89
Example 16 75 C 50 H 34 N 4 691.90
Example 17 76 C 55 H 36 N 4 753.96
Example 18 79 C 55 H 36 N 4 753.98
Example 19 81 C 57 H 40 N 4 782.02
Example 20 84 C 58 H 41 N 3 781.01
Example 21 92 C 57 H 40 N 4 782.04
Example 22 95 C 57 H 40 N 4 782.02
Example 23 100 C 52 H 38 N 4 719.93
Example 24 101 C 57 H 37 N 5 792.99
Example 25 107 C 62 H 39 N 5 855.08
Example 26 113 C 61 H 41 N 5 845.08
Example 27 117 C 66 H 43 N 5 907.18
Example 28 120 C 74 H 50 N 4 996.29
Example 29 131 C 63 H 43 N 3 843.08
Example 30 139 C 68 H 46 N 4 920.19
Example 31 142 C 74 H 47 N 5 1007.28
Example 32 149 C 64 H 46 N 4 872.17
Example 33 153 C 64 H 46 N 4 872.15
Example 34 158 C 70 H 46 N 4 944.21
Example 35 174 C 69 H 45 N 5 945.21
Example 36 182 C 69 H 47 N 3 919.18
Example 37 192 C 69 H 44 N 4 930.17
Example 38 201 C 64 H 39 N 5 879.13
Example 39 212 C 67 H 42 N 4 O 920.16
Example 40 234 C 56 H 38 N 4 768.00
Example 41 248 C 63 H 44 N 4 858.11
Example 42 249 C 64 H 42 N 4 868.11
Example 43 263 C 68 H 44 N 4 918.16
Example 44 270 C 68 H 44 N 4 O 934.17
Example 45 278 C 71 H 47 N 5 971.25
Example 46 283 C 72 H 49 N 5 985.29
Example 47 298 C 67 H 44 N 4 O 922.16
Example 48 303 C 69 H 48 N 4 934.21
Example 49 320 C 73 H 44 N 4 O 2 1010.22
Example 50 339 C 64 H 45 N 3 866.12
Example 51 348 C 68 H 45 N 3 905.16
Example 52 368 C 69 H 45 N 5 945.22
Example 53 377 C 57 H 39 N 3 766.99
Example 54 388 C 67 H 44 N 4 906.17
Example 55 392 C 68 H 46 N 4 920.18
Further, since other compounds of the present invention can be obtained by referring to the synthetic methods of the above-mentioned examples, they are not exemplified herein.
The invention provides an organic electroluminescent device, which specifically can comprise a hole injection layer, a hole transmission layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer, a cap layer and the like as structures of organic layers. In one embodiment, the organic light emitting element may be described as an "organic layer" disposed between the cathode and the anode, which may be achieved by combining the above layers, or some layers may be omitted or added entirely.
According to one embodiment of the present specification, the compound of formula I prepared according to the present invention is used as an electron transport layer material.
The anode is made of a conductor such as a metal, metal oxide, and/or conductive polymer that has a higher work function to aid in hole injection. The metal can be nickel, platinum, vanadium, chromium, copper, zinc, gold, silver or alloys thereof; the metal oxide can be zinc oxide, indium Tin Oxide (ITO) or indium zinc oxide; the combination of metal and oxide can be ZnO and A1 or SnO 2 With SbOr ITO and Ag; the conductive polymer may be selected from poly (3-methylthiophene), poly (3, 4- (ethylene-1, 2-dioxy) thiophene), polypyrrole, and polyaniline, but is not limited thereto.
The hole injection layer and the hole transport layer efficiently inject or transport holes from the anode between the electrodes to which an electric field has been applied, and preferably have high hole injection efficiency and efficiently transport the injected holes. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and which is less likely to cause impurities that become traps during production and use, is preferable. The hole injection layer is preferably a p-doped hole injection layer; the hole transport material may be selected from arylamine derivatives, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like.
A light-emitting auxiliary layer (multi-layer hole transporting layer) is interposed between the hole transporting layer and the light-emitting layer, and functions to smoothly move holes from the anode to the light-emitting layer and block electrons from the cathode.
The light-emitting layer is preferably a compound which emits light by excitation by recombination of holes and electrons, and is preferably a compound which can form a stable thin film shape and exhibits high light-emitting efficiency in a solid state. The light emitting layer may be a single layer or multiple layers and may include a host material and a dopant material. The amounts of the host material and the dopant material to be used may be determined in accordance with the respective material characteristics. The doping method may be realized by co-evaporation with the host material, or may be formed by simultaneous evaporation after mixing with the host material.
The electron transport layer and the electron injection layer efficiently transport or inject electrons from the anode and cathode between the electrodes to which an electric field has been applied. An impurity substance which has a large electron affinity, a large electron mobility, and excellent stability and is not likely to cause a trap is preferable.
The anode is a substance capable of injecting electrons with good efficiency, and the same material as that of the anode can be selected. If a low work function metal is chosen that facilitates efficient electron injection, it is often necessary to dope trace amounts of lithium, cesium or magnesium to avoid its instability in the atmosphere.
There are no particular restrictions on the other layer materials in an OLED device, except that the electron transport layer disclosed in the present invention comprises formula I.
The organic electron transport material and the organic electroluminescent device according to the present invention will be described in detail with reference to specific examples.
Application example 1 preparation of organic electroluminescent device:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. The substrate is used as an anode, a vapor deposition device process is performed by using a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate.
b. HIL (hole injection layer): vacuum evaporation of hole injection layer materials HT and P-dopant at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of HT and P-dopant is 97:3, the thickness is 10nm.
c. HTL (hole transport layer): HT of 120nm was vacuum deposited as a hole transport layer on top of the hole injection layer at a deposition rate of 1.5 Å/s.
d. Prime (light-emitting auxiliary layer): a 10nm prime is vacuum deposited on the hole transport layer as a light emitting auxiliary layer at a deposition rate of 0.5 Å/s.
e. EML (light emitting layer): then, on the above light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant) having a thickness of 25nm were vacuum-evaporated as light-emitting layers at an evaporation rate of 1 Å/s, wherein the ratio of the evaporation rates of Host and Dopant was 97:3.
f. HB (hole blocking layer): a hole blocking layer having a thickness of 5.0nm was vacuum deposited at a deposition rate of 0.5. 0.5 Å/s.
g. ETL (electron transport layer): compound 165 and Liq, which were 35nm thick, were vacuum evaporated as electron transport layers at an evaporation rate of 1 Å/s. Wherein the evaporation rate ratio of compound 165 to Liq is 50:50.
h. EIL (electron injection layer): an electron injection layer was formed by vapor deposition of 1.0nm on a Yb film layer at a vapor deposition rate of 0.5. 0.5 Å/s.
i. And (3) cathode: and evaporating magnesium and silver at 18nm at an evaporation rate ratio of 1 Å/s, wherein the evaporation rate ratio is 1:9, so as to obtain the OLED device.
j. Light extraction layer: CPL with a thickness of 70nm was vacuum deposited as a light extraction layer on the cathode at a deposition rate of 1 Å/s.
k. And packaging the substrate subjected to evaporation. Firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The device structure is as follows:
ITO/Ag/ITO/HT P-dose (10 nm)/HT (120 nm)/prime (10 nm)/Host (dose (25 nm)/HB (5 nm)/ET (compound of the invention): liq (35 nm)/Yb (1 nm)/Mg: ag (18 nm)/CPL (70 nm).
The structural formula of the compound in the device is as follows:
。
application examples 2 to 55
The organic electroluminescent devices of application examples 2 to 55 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 165 of application example 1 was replaced with the corresponding compound of examples 2 to 55, respectively, to form an electron transport layer.
Device comparative examples 1-8:
the organic electroluminescent devices of comparative examples 1 to 8 were prepared according to the above-described preparation method of the organic electroluminescent device, except that the compound 165 of application example 1 was replaced with the comparative compounds 1 to 8, respectively, to form an electron transport layer. Wherein, the structural formula of the comparative compounds 1-8 is as follows:
。
the organic electroluminescent devices obtained in the above device examples 1 to 55 and device comparative examples 1 to 8 were characterized in terms of driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
TABLE 2 luminescence property test results (brightness value 1000 nits)
Note that: bi=light emission efficiency/CIEy in table 2, the light emission efficiency is affected by chromaticity in the blue OLED device.
As can be seen from table 2, the OLED devices prepared using the organic electron transport materials provided in the examples of the present invention were superior in terms of lifetime of devices in the application examples 1 to 55 compared with the conventional OLED devices provided in comparative examples 1 to 8, and the series structures according to the general formula of the present invention improved by 59 to 119 hours as compared with the comparative examples, and increased in light emitting efficiency by 5 to 17% as compared with the comparative examples. Meanwhile, the compounds according to the general formula of the present invention are also improved in BI value and driving voltage as compared with the comparative examples.
The specific compound structure and performance are compared as follows:
；
the structure of the comparative compound 1 is similar to that of the compound 57 in the example provided by the invention, the difference is that the substituted position of 9, 9-diphenyl fluorene in the comparative compound 1 is a benzene ring part in a fluorene ring, the substituted position of 9, 9-diphenyl fluorene in the compound 57 is a phenyl group at the 9 position, and further, the comparison shows that the benzene ring part in the fluorene ring of the comparative compound 1 is bonded with 2-naphthyl, and the compound 57 is bonded with 2-pyridyl on the benzene ring at the 9 position of the fluorene ring. Because naphthyl belongs to electron-rich substituent groups, pyridyl is electron-deficient substituent groups, the bipolar property of the comparative compound 1 is obvious, namely the capability of transporting holes and electrons is equivalent; compound 57 appears to be more electron deficient and is more conducive to electron transport. In addition, the mobility of the organic hole transport material is generally two orders of magnitude higher than that of the organic hole transport material, so that the compound 57 provided by the invention is used as an electron transport material to be more favorable for the recombination of holes and electrons, thereby improving the device efficiency, and as can be seen from Table 2, the luminous efficiency of the compound 57 is improved by 0.85cd/A compared with that of the comparative compound 1.
；
Among them, the structure of the comparative compound 2 is similar to that of the compound 234 in the example provided by the invention, wherein the comparative compound 2 has a1, 4-phenylene group which plays a role in connection in structure, and the compound 234 has a1, 5-naphthylene group, wherein the 1, 4-phenylene group forms a plane with a phenyl group and a biphenyl group substituted triazine part, and the latter has a structure twisted due to substitution on different rings of the naphthyl group, and the 1, 5-naphthyl group is not in the same plane with the phenyl group and the biphenyl group substituted triazine part. Therefore, the compound 234 provided by the invention can avoid the defects of easy stacking, easy aggregation and poor fluidity of molecules caused by a large plane in the molecule in the comparative compound 2, thereby prolonging the service life of the device, and the data in the table 2 shows that the service life of the compound 234 is prolonged by 106h compared with that of the comparative compound 2, and in addition, the compound 234 is more beneficial to electron transmission due to the fact that the electron-withdrawing 3-pyridyl group is introduced into the compound 234, so that the efficiency of the device is also enhanced by 0.72cd/A. Similarly, the 337 structure provided by the invention is also significantly improved in terms of device lifetime and luminous efficiency over comparative compound 3.
；
Wherein, the structure of the comparative compound 4 is similar to that of the compound 368 in the examples provided by the invention, the 3-phenyl-9, 9-dimethylfluorenyl and 2, 4-diphenyl-1, 3, 5-triazinyl are bridged by 3,3'-1,1' -diphenyl in the comparative compound 4, and the 2, 4-diphenyl-1, 3, 5-triazinyl and other groups are bridged by 1, 7-naphthyl and 3,3'-1,1' -diphenyl in the comparative compound 368. The position of biphenyl group in the comparison compound is a diagonal position, so that the space three-dimensional property of the structure is poor, the compound 368 enhances the torsion of the configuration by introducing 1, 7-naphthyl, reduces the defects of poor film forming property and short service life of a device caused by molecular aggregation and crystallization, and simultaneously, the compound 368 introduces a strong electron-withdrawing group 2-cyano-4-phenylpyridyl, so that the electron transmission performance is obviously enhanced. As can be seen from Table 2, the lifetime of compound 368 is increased by 101h, and the luminous efficiency is improved by 0.74cd/A.
；
Wherein, comparing the structure of the comparative compound 5 with that of the compound 192 in the embodiment provided by the invention, the 4-position of 9, 9-diphenyl fluorene is substituted in the comparative compound 5, and the meta position of the same 9-position phenyl of 9, 9-diphenyl fluorene in the compound 192 is substituted by a group, so that the molecular structure is twisted, the intermolecular interaction force is weakened, and the service life of the device is prolonged by 90 hours relative to that of the comparative compound 5.
；
The structure of the compound 278 in the comparative compound 6 is similar to that of the compound 278 in the embodiment provided by the invention, but the 9, 10-anthrylene group and the bonded spirobifluorene group in the comparative compound 6 perform better in the aspect of hole transmission, so that the compound 278 has bipolar property, the bonding of the 9, 9-diphenyl fluorene 9-position phenyl group and the 3-cyanopyridine group in the meta position of the 9-benzene ring are bonded, and the electron-withdrawing characteristic of pyridine and cyano group makes the electron transmission property of the whole compound 278 stronger than that of the compound 6, so that the hole and electron recombination is facilitated, the device efficiency is improved, and the service life of the device is prolonged.
；
The structure of the comparative compound 7 is similar to that of the compound 33 in the embodiment provided by the invention, but the present invention is substituted on the same benzene ring at 9 position of 9, 9-diphenyl fluorene, and the comparative compound 7 is substituted on two benzene rings at 9 position respectively, so that the structural symmetry is better than that of the compound 33, thereby leading to easy stacking of molecules and reducing the service life of the device, and compared with the comparative compound 7, the service life of the compound 33 is improved by 73h as shown in table 2.
；
The structure of the comparative compound 8 is similar to that of the compound 56 in the embodiment provided by the invention, but the substitution is carried out on the same benzene ring at the 9 position of 9, 9-diphenyl fluorene, and the comparative compound 8 is respectively substituted on two benzene rings at the 9 position, so that the structural symmetry of the compound is better than that of the compound 56, the molecules are easy to stack, the service life of the device is reduced, and the service life of the device is reduced by 100h compared with that of the compound 56. In addition, the structure in which only phenylene-naphthyl-phenyl is introduced into the benzene ring at the 9-position in the comparative compound 8, and the electron withdrawing group is not present, so that the whole molecule has poor electron transmission, the driving voltage is increased by 0.08V relative to the compound 56, and the efficiency is reduced by 0.47cd/A.
In conclusion, the sp of the 9 position of the fluorene ring of the organic electronic transmission material provided by the invention 3 The hybridized carbon maintains the spatial configuration of the compound; the bridged substituted heteroaryl enables the compound to have electron-withdrawing property, is favorable for electron transmission, enhances the recombination of electrons and holes in the light-emitting layer, and thus improves the light-emitting efficiency of the device; substitution of heteroaryl at different positions of phenyl or naphthyl further avoids the occurrence of large planes in the molecule to enhance intermolecular interactions, resulting in shortened device lifetime; meanwhile, the heteroaryl groups are bridged at different positions of the 9-position benzene ring of fluorene, so that the reduction of electron transmission caused by bipolar molecular property can be avoided.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. An organic electron transport material characterized by having a structure represented by formula I:
wherein,,
Z 1 ～Z 3 independently represent C, N atoms, Z 1 ～Z 3 Wherein the number of N is 2 or 3;
Z 4 ～Z 9 independently represent C, N atoms, Z 4 ～Z 9 Wherein N numbers are integers of 0-3;
r is independently selected from hydrogen, cyano, methyl, ethyl, n-propyl, isopropyl, phenyl, triazinyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl;
a is an integer of 1 to 5;
and when Z is 4 ～Z 9 When the two are C atoms, R has at least one strong electron withdrawing group selected from cyano, triazine, pyridazine, pyrimidine, pyrazine and pyridine;
R 1 independently represents methyl, ethyl, phenyl;
m, n independently represent integers of 0, 1, 2;
Ar 1 ，Ar 2 independently represent phenyl, biphenyl, terphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl and dibenzothiophenyl.
2. The organic electron transport material according to claim 1, wherein Z 1 ～Z 3 Are all N;
r represents cyano, methyl, phenyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl;
R 1 represented by methyl, phenyl;
m, n independently represent 0 or 1;
Ar 1 ，Ar 2 independently represents phenyl biphenyl group,Naphthyl, 9-dimethylfluorenyl, and combinations thereof.
3. The organic electron transport material according to claim 2, wherein R represents cyano, methyl, phenyl, pyridyl;
Ar 1 ，Ar 2 independently represents phenyl, biphenyl, naphthyl;
the general formula I includes the following structure:
4. the organic electron transport material according to claim 1, wherein the organic electron transport material is selected from any one of the compounds represented by the following structural formulas:
5. a method for preparing an organic electron transport material according to any one of claims 1 to 4, comprising the steps of:
(1)N 2 under the protection, adding 1.0 equivalent of reactant 1, 1.3-1.5 equivalent of reactant 2, 0.01-0.02 equivalent of palladium catalyst and 2.0-2.3 equivalent of alkali into a mixed solvent of toluene, ethanol and water respectively, heating to 80-100 ℃, reacting for 8-10 hours, cooling to room temperature, adding water, filtering after solid precipitation is finished, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain an intermediate 1;
(2)N 2 under the protection, adding 1.0 equivalent of the intermediate 1, 1.0-1.2 equivalent of the reactant 3, 0.01-0.02 equivalent of the palladium catalyst and 2.0-2.3 equivalent of the alkali into a mixed solvent of toluene, ethanol and water respectively, heating to 80-100 ℃, reacting for 8-12 hours, cooling to room temperature, adding water, filtering after the solid is separated out, drying a filter cake, purifying the residual substances by using a column chromatography, removing the solvent from the filtrate by using a rotary evaporator, and drying the obtained solid to obtain the formula I;
the specific synthetic route is as follows:
wherein reactant 1 and reactant 3 can be obtained from known starting materials or synthesized by:
under the protection of nitrogen, 1.0 equivalent of reactant b, 1.5-1.8 equivalent of reactant a, 0.05-0.1 equivalent of palladium catalyst and 2.0-3.0 equivalent of potassium acetate are dissolved in N, N-Dimethylformamide (DMF), the temperature is raised to 85-95 ℃, the reaction is carried out for 8-12 hours, a rotary evaporator is used for removing the solvent, methylene dichloride is added into residues for stirring and filtering, and the residual substances are purified by a column chromatography, thus obtaining the reactant 1;
synthesizing a reactant 3 according to the method for synthesizing the reactant 1, and replacing the reactant a with a reactant c to obtain the catalyst;
hal is selected from Cl, br; hal1 is selected from Br, I;
r' is
A is boric acid or pinacol ester of biboric acid;
R、R 1 、Ar 1 ～Ar 2 、Z 1 ～Z 3 、Z 4 ～Z 9 and m, n have the meanings given in claim 1。
6. The method for producing an organic electron transport material according to claim 5, wherein the palladium catalyst is selected from the group consisting of Pd 2 (dba) 3 ，Pd(PPh 3 ) 4 ，PdCl 2 ，PdCl 2 (dppf)，Pd(OAc) 2 ，Pd(PPh 3 ) 2 Cl 2 ，NiCl 2 (dppf); the base is selected from K 2 CO 3 ，K 3 PO 4 ，Na 2 CO 3 ，CsF，Cs 2 CO 3 ，t-BuONa。
7. Use of an electron transport material according to any of claims 1 to 4 or prepared by a method according to any of claims 5 to 6 for the preparation of an organic electroluminescent device.
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CN115745977A (en) * 2023-01-10 2023-03-07 吉林奥来德光电材料股份有限公司 Electron transport material, preparation method thereof and organic electroluminescent device

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CN110785409A (en) * 2017-07-28 2020-02-11 株式会社Lg化学 Fluorene derivative and organic light emitting device comprising the same
CN110785411A (en) * 2017-07-28 2020-02-11 株式会社Lg化学 Fluorene derivative and organic light emitting device comprising the same
CN115745977A (en) * 2023-01-10 2023-03-07 吉林奥来德光电材料股份有限公司 Electron transport material, preparation method thereof and organic electroluminescent device

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