CN111187201A - Compound and organic electroluminescent device - Google Patents

Compound and organic electroluminescent device Download PDF

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CN111187201A
CN111187201A CN202010074641.7A CN202010074641A CN111187201A CN 111187201 A CN111187201 A CN 111187201A CN 202010074641 A CN202010074641 A CN 202010074641A CN 111187201 A CN111187201 A CN 111187201A
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段炼
张东东
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Tsinghua University
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Abstract

The invention provides a novel compound, in particular to a compound containing an anthracene structure connected with a heterocyclic structure, and also relates to application of the compound in an organic electroluminescent device. The novel organic electroluminescent material of the present invention is represented by the following formula (I).

Description

Compound and organic electroluminescent device
Technical Field
The invention relates to a novel compound, in particular to a compound containing an anthracene structure connected with a heterocyclic structure, and also relates to application of the compound in an organic electroluminescent device.
Background
Balanced electron and hole transport is a guarantee of high efficiency and long lifetime for Organic Light Emitting Diode (OLED) technology. The mobility of the electron transport material (ETL) is relatively low with respect to the commonly used hole transport material (HTL). The anthracene-based transport materials have been documented to have a high electron transport capacity, due to the fact that the large conjugated planes of the anthracene core facilitate orbital overlap between the materials, thereby increasing mobility. And for anthracene electron transport materials, the optimization of side chain groups can obviously improve the performance of the materials. On the one hand, the side chain having a nitrogen-containing heterocyclic group can deepen the LUMO level of the anthracene-based ETM to facilitate electron injection; on the other hand, the side chain group can adjust the molecular distance between anthracene planes, thereby adjusting the electron transport property.
However, one significant problem with anthracene-based ETMs is that they have low triplet states and thus, when re-applied to phosphorescent or thermally activated delayed fluorescence devices, quench excitons in the light emitting layer, thereby reducing device efficiency. Therefore, for anthracene ETM, how to improve the mobility of the material and simultaneously, suppressing exciton quenching is the key to further improve the device performance.
Disclosure of Invention
In view of the above-described problems of the prior art, an object of the present invention is to provide a novel electron transport material containing an anthracene structure, which can achieve both transport performance and exciton blocking performance of the material. The organic electroluminescent device can be used for an organic electroluminescent device so as to meet the requirement of continuously improving the photoelectric property of an OLED device.
The inventor of the invention finds a novel compound containing an anthracene structure, and finds that good electron injection and transmission performance and exciton blocking can be realized by adjusting a substituent group on a mother nucleus containing the anthracene structure and introducing the substituent group into an organic electroluminescent device.
As one aspect of the present invention, there is provided a compound represented by the following formula (I),
Figure BDA0002378178460000011
in the formula (I), X1～X5Are identical to or different from each other, and X1～X5Each independently represents CR1Or N, and at least one is N;
R1any one selected from the group consisting of hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 cycloalkyl groups, substituted or unsubstituted C1-C10 chain alkoxy groups, substituted or unsubstituted C3-C10 cycloalkoxy groups, halogens, cyano groups, nitro groups, hydroxyl groups, silane groups, amino groups, and substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C6-C30 arylamino groups, substituted or unsubstituted C3-C30 heteroarylamino groups, and substituted or unsubstituted C3-C30 heteroaryl groups, and R is hydrogen, substituted or unsubstituted C1-C10 chain alkyl groups, substituted or unsubstituted C3-C10 chain alkoxy groups, and R is hydrogen, substituted or unsubstituted C30 heteroaryl groups1May be fused to the attached heteroaromatic ring to form a ring;
r1 and R2 each represent a single substituent up to the maximum allowable number of substituents, and are each independently selected from any one of hydrogen, substituted or unsubstituted C1 to C10 chain alkyl groups, substituted or unsubstituted C3 to C10 cycloalkyl groups, substituted or unsubstituted C1 to C10 chain alkoxy groups, substituted or unsubstituted C3 to C10 cycloalkoxy groups, halogen, cyano groups, nitro groups, hydroxyl groups, silyl groups, amino groups, and substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C3 to C30 heteroarylamino groups, and substituted or unsubstituted C3 to C30 heteroaryl groups;
ar is selected from any one of the structures represented by the following formulae (1) to (7):
Figure BDA0002378178460000021
in formulae (1) to (7), X1～X33Are identical to or different from each other, and X1～X33Each independently represents CR2Or N, R2Any one selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 chain alkoxy, substituted or unsubstituted C3-C10 cycloalkoxy, halogen, cyano, nitro, hydroxyl, silane, amino and substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, and substituted or unsubstituted C3-C30 heteroaryl;
in formulae (1) to (7), A1～A8The aryl group is any one of hydrogen, halogen, cyano, hydroxyl, substituted or unsubstituted amino, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
in the formulae (1) to (7), n1 to n7 are each independently selected from integers of 0 to 2;
when each of the above groups independently has a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, hydroxyl, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C2-C10 alkenyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl or C6-C30 fused ring heteroaryl.
Further preferably, X in the compound of formula (I) according to the invention1～X5At least two of which are N.
Further preferably, X in the compound of formula (I) according to the invention3And X4At least one of (A) and (B) is N, particularly preferably X3Is N, or preferably X4Is N, or preferably X3And X4And is also N.
Further preferably, Ar in the compound of formula (I) of the present invention is selected from any one of the structures represented by formula (1), formula (2) or formula (3).
Specifically, when the hexatomic ring serving as the outermost side in the structure of the formula (I) contains only one nitrogen atom, the inventors found that the compound can provide better electron transport performance when used in an organic electroluminescent device, and speculate that the nitrogen atom is located outside the material, and the nitrogen atom is easy to generate more obvious hydrogen bond interaction with an anthracene ring with a larger conjugated structure, so that the electron mobility of the organic electroluminescent material is improved, the injection of electrons is facilitated, the driving voltage is reduced, and the luminous efficiency is improved.
Further, among the compounds represented by the formula (I) of the present invention, X is also preferable1～X5At least two of which are nitrogen atoms, can provide better electron transport properties. It is presumed that when two or more nitrogen atoms are present in the outermost six-membered ring, the compound as a whole has a higher electron affinity and a stronger ability to accept electrons, and therefore, contributes to further reduction in driving voltage and improvement in light emission efficiency.
Still further, in the compounds of the present invention, R1And R2Each independently is preferably selected from the following groups:
Figure BDA0002378178460000031
in the present specification, unless otherwise indicated, the following terms have the following meanings:
the symbol denotes the position bonded to the linking group, "-" denotes the expression of the ring structure, and denotes that the linking site is located at any position on the ring structure that is capable of forming a bond.
The expression Ca to Cb means that the group has carbon atoms a to b, and the number of carbon atoms does not generally include the number of carbon atoms of the substituent unless otherwise specified. In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium". In the present invention, "D" may be used to represent "deuterium".
In the present specification, examples of the C1-C12 alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, among which methyl, ethyl, n-propyl, isopropyl are preferred, and methyl is more preferred;
examples of the C1-C12 alkoxy group include groups obtained by linking the above-mentioned C1-C12 alkyl group with-O-, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc., among which methoxy, ethoxy, propoxy and more preferably methoxy are preferable;
examples of C6-C30 arylamino groups include: phenylamino, diphenylamino, biphenylylamino, terphenylamino, naphthylamino, anthrylamino, phenanthrylamino, fluorenylamino, pyrenylamino,
Figure BDA0002378178460000032
Arylamino, fluoranthenylamino, picrylamino, peryleneamino, etc., and among them, diphenylamino is preferable;
examples of C3-C30 heteroarylamino groups are: pyridylamino, pyrimidylamino, pyrazinylamino, pyridazinylamino, quinolylamino, isoquinolylamino, acridinylamino, pyrrolylamino, imidazolylamino, pyrazolylamino, indolylamino, benzimidazolylamino, carbazolylamino, furanylamino, thienylamino, thiazolylamino, benzofuranylamino, benzothienylamino, benzothiazolylamino, dibenzofuranylamino, dibenzothiophenylamino, piperidinylamino, pyrrolidinylamino and the like, with pyridylamino being preferred;
examples of C6-C30 aryl groups include: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthrylFluorenyl, pyrenyl,
Figure BDA0002378178460000042
Fluoro, anthryl, benzo [ a ]]Anthracenyl, benzo [ c ]]Phenanthryl, triphenylene, benzo [ k ]]Fluoranthenyl, benzo [ g ]]
Figure BDA0002378178460000043
Radical, benzo [ b]Triphenylene, picene, perylene, etc., of which phenyl and naphthyl are preferred, and phenyl is more preferred;
the heteroaryl group having C3 to C30 may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, or the like, and specific examples thereof include: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, naphthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, indolyl, benzimidazolyl, indazolyl, imidazopyridinyl, benzotriazolyl, carbazolyl, furyl, thienyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, benzofuranyl, benzothienyl, benzoxazolyl, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzoxadiazolyl, benzothiadiazolyl, dibenzofuranyl, dibenzothienyl, piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like are preferred among them, pyridyl, quinolyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, and the like, Dibenzofuranyl and dibenzothienyl, and more preferably pyridyl.
Preferred structures of the compounds according to the present invention include, but are not limited to, the compounds having the following structures.
Figure BDA0002378178460000041
Figure BDA0002378178460000051
Figure BDA0002378178460000061
Figure BDA0002378178460000071
Figure BDA0002378178460000081
Figure BDA0002378178460000091
Figure BDA0002378178460000101
Figure BDA0002378178460000111
Figure BDA0002378178460000121
Figure BDA0002378178460000131
Figure BDA0002378178460000141
Figure BDA0002378178460000151
Figure BDA0002378178460000161
Figure BDA0002378178460000171
Figure BDA0002378178460000181
Figure BDA0002378178460000191
Figure BDA0002378178460000201
Figure BDA0002378178460000211
As another aspect of the present invention, there is also provided a use of the compound as described above in an organic electroluminescent device. The compound has a larger conjugated structure, can realize good electron injection and transmission performance when being used as an electron transmission material, and further can obtain an organic electroluminescent device with low driving voltage and high luminous efficiency. Of course, since the compound of the present invention has a higher electron affinity, it can also be used as a material for a hole-blocking layer.
The compound can be independently used in a hole blocking layer and an electron transport layer, and can provide more excellent device performance compared with the existing material. The compound of the invention can also be used by being matched with the existing electron transport material or hole blocking material, and can also bring excellent device performance.
The use of the compound of the present invention as an electron transport material or a hole blocking material is not limited to the field of organic electroluminescence, and the compound can be applied to organic electronic devices, for example, organic electroluminescent devices, lighting devices, organic thin film transistors, organic field effect transistors, organic thin film solar cells, large-area sensors such as information tags, electronic artificial skin sheets and sheet-type scanners, electronic paper, organic EL panels, and the like.
Specifically, one embodiment of the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise at least a light-emitting layer, and the organic layers comprise a compound of the present invention.
Further, as the organic layer between the first electrode and the second electrode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and the like are generally included, and among them, the organic layer containing the compound of the present invention can be used as, but not limited to, an electron transport layer.
The compound has very excellent performance, is particularly preferably used as a transmission material when being used in an organic electroluminescent device, and has excellent electron injection, transmission capability and exciton blocking performance. The specific reason is not clear, and it is presumed that the following may be the reason:
the side chain groups connected with the 9 and 10 sites of the anthracene of the mother nucleus structure of the compound of the general formula are nitrogen-containing heterocycles, so that strong intermolecular hydrogen bonds are introduced, the deposition of the anthracene structure center is facilitated, the whole compound has higher electron affinity, the compound is very suitable for the flow of electrons in the compound, and simultaneously, the compound is closer to the work function of a cathode material, so that the material can easily obtain electrons from the cathode, and the compound has strong electron injection property. On the other hand, hydrogen bonds more easily cause the compound to form a more tightly packed structure as a whole, making the compound chemically more stable as a whole, thereby improving the life of the compound.
One side chain of the anthracene with the mother nucleus structure of the compound in the general formula is a linear small steric hindrance structure adopting a benzene ring connected with a nitrogen heterocycle, wherein the nitrogen heterocycle is designed at the outermost side, so that intermolecular hydrogen bonds can be further introduced, the central distance of the anthracene is reduced, the material is favorably compacted, the compound molecules can fully generate pi-pi interaction between groups in a solid state, the transmission of electrons between the material molecules is favorably realized, the electron mobility is improved, and meanwhile, the anthracene with the mother nucleus structure has the other side chain L of the anthracene with the mother nucleus structure cooperatively designed1The 7 groups are groups with larger steric hindrance and high triplet state, and the nitrogen atom can be introduced into intermolecular hydrogen bond, which is favorable for obtainingA tight molecular arrangement. And the high-steric-hindrance high-triplet-state side chain group can coat an anthracene core with low triplet state, so that high-triplet-state excitons in a triplet-state quenching light-emitting layer with low anthracene center can be prevented, and the exciton blocking performance of ETM is improved.
Therefore, the novel compound can further optimize electron injection and transmission capacity and good exciton blocking performance, has very remarkable and excellent electron mobility, and has good film forming performance when being applied to an organic layer of an organic electroluminescent device, so that the efficiency and the stability of an electron transmission layer can be improved. The device adopting the compound has the advantages of high luminous efficiency, low driving voltage and long service life.
Detailed Description
In order to make those skilled in the art better understand the present invention, the following will describe the specific preparation method of the above compound of the present invention by taking several synthetic examples as examples, but the preparation method of the present invention is not limited to these several synthetic examples, and those skilled in the art can make any modification, equivalent substitution, improvement, etc. without departing from the principle of the present invention, and extend the method to the scope of the technical scheme of the present invention as claimed in the claims.
The basic chemical materials of various chemicals used in the present invention, such as petroleum ether, ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, potassium phosphate, sodium tert-butoxide, etc., are commercially available from commercial chemical suppliers, including but not limited to Shanghai Tantake technology, Inc. and Xilonga chemical, Inc. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK). In the present invention, nuclear magnetic resonance was measured using a BRUKER 500MHZ nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany).
Synthetic examples
Synthesis example 1: synthesis of Compound C1
Figure BDA0002378178460000231
Preparation of intermediate 1:
under the protection of nitrogen, 30g (85.96mmol, 1eq) of the compound 1- (4-bromophenyl) -2-phenyl-1H-benzo [ d ] imidazole is added into 300mL of tetrahydrofuran in a 1000mL three-necked bottle, the temperature is reduced to minus 78 ℃, 39.4mL (94.56mmol, 1.1eq) of n-BuLi is slowly dropped into the reaction solution, the reaction solution is kept for 1.5H, then 32.3g (171.92mmol, 2eq) of triisopropyl borate is slowly dropped into the reaction solution, the temperature is naturally raised to room temperature, the stirring is carried out overnight, the reaction is stopped, 100mL of 1mol/L diluted hydrochloric acid solution is added, the stirring is carried out for 1H at normal temperature, the liquid separation is carried out, the aqueous phase is extracted by 200mL of dichloromethane, the organic phases are combined, and the rotary drying is carried out to obtain 21.67g of white solid with the yield of 80%.
Preparation of intermediate 2:
under the protection of nitrogen, 20g (100mmol, 1eq) of 4- (3-pyridine) -6-phenylboronic acid, 26g (100mmol, 1eq) of 9-bromophenanthrene and 42g (300mmol, 3eq) of potassium carbonate are added into a 1000ml three-neck flask and dissolved in 200ml of toluene, 100ml of ethanol and 100ml of water, tetrakis (triphenylphosphine) palladium is added after nitrogen is replaced, heating reflux reaction is carried out overnight, the reaction of 2-phenyl-5-pyridine borate serving as a raw material is finished, the temperature is reduced to room temperature, liquid separation is carried out, toluene is used for extraction and drying, a column is passed, an organic phase is dried in a spinning mode, a solid is obtained, and then 200ml of petroleum ether is used for boiling and washing to obtain 14g of light yellow solid powder, wherein.
Preparation of intermediate 3:
14g (42mmol, 1eq) of intermediate 2 were dissolved in 100ml of DMF at room temperature in a 500ml three-necked flask, and NBS7.9g (44mmol, 1.05eq) of DMF50ml was added dropwise, the reaction was carried out overnight at room temperature, the reaction was completed on a plaque, the mixture was poured into 300ml of water with stirring, and the mixture was filtered with suction to obtain a yellow solid which was recrystallized from petroleum ether.
Preparation of compound C1:
adding 8.35g (20.36mmol, 1eq) of compound 3, 6.67g (21.38mmol, 1.05eq) of compound 1, 8.43g (61.09mmol, 3eq) of potassium carbonate into a 1000mL three-necked bottle under the protection of nitrogen, putting into a reaction bottle, then adding 90mL of toluene, 45mL of ethanol and 45mL of water, starting stirring, adding 0.235g (0.204mmol, 0.01eq) of tetratriphenylphosphonium palladium into the mixture after blowing nitrogen for 20min, heating and refluxing for reaction overnight, spotting until the intermediate 1 is basically completely reacted, stopping the reaction, extracting 300mL of cooled liquid-separating water phase with DCM, combining organic phases, drying, spinning, dissolving solid with DCM, stirring silica gel, passing through the column to obtain 8.54 g of pure product with the yield of 70%
Product MS (m/e): 600.3,1HnmR(400MHz,CDCl3)δ8.36(s,4H),8.29(s,1H),7.55(s,3H),7.50(s,6H),7.32(d,J＝21.1Hz,1H),7.21(dd,J＝32.0,8.0Hz,8H),7.08(s,4H),7.00(s,2H).
synthesis example 2: synthesis of Compound C6
Figure BDA0002378178460000241
Preparation of intermediate 4:
the synthesis steps are the same as those of the intermediate 2, except that 4- (3-pyridine) -6-phenylboronic acid is changed into 4- (4-pyridine) -6-phenylboronic acid, and other reagents are not changed, so that the intermediate 4 is obtained, and the yield is 78%.
Preparation of intermediate 5:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 4 and the other reagents were unchanged to give intermediate 5 in 48% yield.
Preparation of compound C6:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 5 and the other reagents were unchanged to give compound C6 with a yield of 76%.
Product MS (m/e): 600.3,1HnmR(400MHz,CDCl3)δ8.38(s,4H),8.26(s,1H),7.53(s,3H),7.51(s,6H),7.34(d,J＝21.1Hz,1H),7.20(dd,J＝32.0,8.0Hz,8H),7.10(s,4H),6.95(s,2H).
synthetic example 3: synthesis of Compound C18
Figure BDA0002378178460000242
Preparation of intermediate 6:
the synthesis procedure was the same as intermediate 2 except that 4- (3-pyridine) -6-phenylboronic acid was changed to [4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl ] boronic acid and the other reagents were unchanged to give intermediate 6 in 42% yield.
Preparation of intermediate 7:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 6 and the other reagents were unchanged to give intermediate 7 in 77% yield.
Preparation of compound C18:
the synthesis procedure was identical to that of compound C6 except that intermediate 5 was changed to intermediate 7, intermediate 1 was changed to 4- (4-pyridine) -6-phenylboronic acid, and the other reagents were unchanged to give compound C18 in 79% yield.
Product MS (m/e): 639.3,1HnmR(400MHz,CDCl3)δ8.69(s,2H),8.26(s,4H),8.18(s,4H),7.90(s,4H),7.44(d,J＝17.1Hz,6H),7.28(dd,J＝22.0,10.1Hz,4H),7.17(s,6H).
synthetic example 4: synthesis of Compound C5
Figure BDA0002378178460000251
Preparation of intermediate 8:
the synthesis steps are the same as those of the intermediate 2, except that 4- (3-pyridine) -6-phenylboronic acid is changed into 4- (5-pyrimidine) -6-phenylboronic acid, and other reagents are not changed, so that an intermediate 8 is obtained, and the yield is 58%.
Preparation of intermediate 9:
the synthesis procedure was the same as intermediate 1 except that intermediate 2 was changed to intermediate 8 and the other reagents were unchanged to give intermediate 9 in 87% yield.
Preparation of compound C5:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 9 and the other reagents were unchanged to give compound C5 with a yield of 79%.
Product MS (m/e): 601.2,1HnmR(400MHz,CDCl3)δ9.40(s,1H),9.18(s,2H),8.56(d,J＝20.5Hz,1H),8.28(s,6H),7.87(s,5H),7.50(d,J＝19.1Hz,4H),7.25(dd,J＝32.0,8.0Hz,9H).
synthesis example 5: synthesis of Compound C130
Figure BDA0002378178460000252
Preparation of intermediate 10:
the synthesis steps are the same as the intermediate 1, except that 1- (4-bromophenyl) -2-phenyl-1H-benzo [ d ] imidazole is changed into 2- (4-bromophenyl) phenanthro [9,10-B ] pyrazine, other reagents are not changed, and the intermediate 10 is obtained with the yield of 75%.
Preparation of intermediate 11:
the synthesis steps are the same as those of the intermediate 2, except that 4- (3-pyridine) -6-phenylboronic acid is changed into 4- (2-pyridyl) phenylboronic acid, and other reagents are not changed, so that the intermediate 11 is obtained, and the yield is 66%.
Preparation of intermediate 12:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 11 and the other reagents were unchanged to give intermediate 12 in 77% yield.
Preparation of compound C130:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 12, intermediate 1 was changed to intermediate 10, and the other reagents were unchanged to give compound C130 in 65% yield.
Product MS (m/e): 636.2,1HnmR(400MHz,CDCl3)δ9.00(d,J＝31.0Hz,2H),8.91(d,J＝28.8Hz,2H),8.66(d,J＝27.5Hz,3H),8.28(s,1H),8.22(d,J＝24.5Hz,4H),8.12(d,J＝22.7Hz,2H),7.65(d,J＝19.1Hz,4H),7.33(m,9H),7.14(s,1H),6.95(s,1H).
synthetic example 6: synthesis of Compound C10
Figure BDA0002378178460000261
Preparation of intermediate 13:
the synthesis procedure was the same as intermediate 1 except that 1- (4-bromophenyl) -2-phenyl-1H-benzo [ d ] imidazole was changed to 2- (4-bromophenyl) -1-phenyl-1H-benzimidazole and the other reagents were unchanged to give intermediate 13 in 83% yield.
Preparation of intermediate 14:
the synthesis procedure is the same as that of intermediate 2, except that 4- (3-pyridine) -6-phenylboronic acid is changed into 4- (4-pyridyl) phenylboronic acid, and other reagents are not changed, so that intermediate 14 is obtained with the yield of 78%.
Preparation of intermediate 15:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 14 and the other reagents were unchanged to give intermediate 15 in 65% yield.
Preparation of compound C10:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 15, intermediate 1 was changed to intermediate 13, and the other reagents were unchanged to give compound C10 with a yield of 69%.
Product MS (m/e): 600.3,1HnmR(400MHz,CDCl3)δ8.44(s,4H),8.24(s,1H),7.55(s,3H),7.50(s,6H),7.32(d,J＝20.9Hz,1H),7.20(dd,J＝31.6,7.9Hz,8H),7.11(s,4H),6.94(s,2H).
synthetic example 7: synthesis of Compound C146
Figure BDA0002378178460000271
Preparation of intermediate 16:
the synthesis procedure was the same as intermediate 1 except that 1- (4-bromophenyl) -2-phenyl-1H-benzo [ d ] imidazole was changed to 2- (4-bromophenyl) -4-phenylbenzo [ H ] quinazoline and the other reagents were unchanged to give intermediate 16 in 75% yield.
Preparation of intermediate 17:
the synthesis procedure was the same as intermediate 2 except that 4- (3-pyridine) -6-phenylboronic acid was changed to (4- (pyridazin-3-yl) phenyl) boronic acid and the other reagents were unchanged to give intermediate 17 in 82% yield.
Preparation of intermediate 18:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 17 and the other reagents were unchanged to give intermediate 18 in 70% yield.
Preparation of compound C41:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 18, intermediate 1 was changed to intermediate 16, and the other reagents were unchanged to give compound C41 with a yield of 60%.
Product MS (m/e): 663.3,1HnmR(400MHz,CDCl3)δ8.98(s,1H),8.51(s,1H),8.24(s,6H),8.10(s,1H),8.00(s,3H),7.75(s,8H),7.49(d,J＝21.9Hz,1H),7.25(dd,J＝29.0,7.9Hz,9H).
synthesis example 8: synthesis of Compound C143
Figure BDA0002378178460000281
Preparation of intermediate 19:
the synthesis procedure was the same as intermediate 1 except that 1- (4-bromophenyl) -2-phenyl-1H-benzo [ d ] imidazole was changed to 2- (4-bromophenyl) -4-phenylquinazoline and the other reagents were unchanged to give intermediate 19 in 55% yield.
Preparation of intermediate 20:
the synthesis procedure was the same as intermediate 2 except that 4- (3-pyridine) -6-phenylboronic acid was changed to (4- (pyridazin-4-yl) phenyl) boronic acid and the other reagents were unchanged to give intermediate 20 in 86% yield.
Preparation of intermediate 21:
the synthesis procedure was the same as intermediate 3 except that intermediate 2 was changed to intermediate 20 and the other reagents were unchanged to give intermediate 21 in 64% yield.
Preparation of compound C143:
the compound C1 was synthesized in the same procedure except that intermediate 3 was changed to intermediate 18, intermediate 1 was changed to intermediate 16, and the other reagents were unchanged to give compound C143 in 55% yield.
Product MS (m/e): 613.2,1HnmR(400MHz,CDCl3)δ9.50(s,1H),9.37(s,1H),8.24(s,5H),7.85(s,6H),7.80(s,6H),7.65(s,4H),7.37(d,J＝28.9Hz,4H),7.25(d,J＝29.0,6H).
the compound of the present invention can be obtained by the above-described synthesis method, but is not limited to these methods. Other methods known to those skilled in the art, such as Stille coupling, Grignard reagent, etc., can be selected by those skilled in the art, and any equivalent synthetic method can be used for the purpose of achieving the objective compound preparation, and can be selected as desired.
Next, embodiments of the organic electroluminescent device prepared using the compound of the present invention will be described in detail.
The organic electroluminescent device includes first and second electrodes on a substrate, and an organic layer between the electrodes, which may be a multi-layered structure. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
As the substrate, a substrate used for a general organic light emitting display, for example: glass, polymer materials, glass with TFT components, polymer materials, and the like.
The anode material can be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin dioxide (SnO)2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of these materials.
The cathode material can be selected from metals, metal mixtures and oxides such as magnesium silver mixture, LiF/Al, ITO and the like.
The organic electroluminescent device may further include a hole transport layer and a hole injection layer between the light emitting layer and the anode, and these layers may include one or more combinations of compounds HT1-HT34 listed below, but are not limited to the following compounds.
Figure BDA0002378178460000291
Figure BDA0002378178460000301
The light emitting layer of the organic electroluminescent device may include a host material and a light emitting dye, wherein the host may be one or a combination of more of the compounds BFH1-BFH14 listed below, but is not limited to the following compounds.
Figure BDA0002378178460000302
Figure BDA0002378178460000311
The luminescent dye may be a combination of one or more of the compounds BFD1-BFD9 listed below, but is not limited to the following compounds.
Figure BDA0002378178460000312
The organic layer of the organic electroluminescent device may include an electron transport layer, and a hole blocking layer between the light emitting layer and the electron transport layer. The compound can be independently used in a hole blocking layer and an electron transport layer, and can provide more excellent device performance compared with the existing material. The compound of the invention can also be used by being matched with the existing electron transport material or hole blocking material, and can also bring excellent device performance. For example, the compounds of the present invention can achieve very good device performance when complexed with liq. In addition, the hole blocking layer and the electron transport layer materials that can be used in combination with the compounds of the present invention may be one or a combination of more of the compounds ET1-ET57 listed below, but are not limited to the following compounds.
Figure BDA0002378178460000313
Figure BDA0002378178460000321
Figure BDA0002378178460000331
Figure BDA0002378178460000341
When the compound of the present invention is used in combination with other existing materials, the compounding ratio of the compound of the present invention may be 1 to 99% by weight, preferably 30 to 75% by weight, and more preferably 40 to 60% by weight.
An electron injection layer may also be included in the organic electroluminescent device between the electron transport layer and the cathode, the electron injection layer material including a combination of one or more of the following listed materials, but not limited to the following: LiQ, LiF, NaCl, CsF, Li2O、Cs2CO3、BaO、Na、Li、Ca。
Application examples
The technical effects and advantages of the present invention are demonstrated and verified by testing practical use performance by specifically applying the compound of the present invention to an organic electroluminescent device.
For the purpose of comparing device application properties of the light emitting materials of the present invention, compounds ET-58 and ET-59 shown below were used as comparative materials.
(A) Preparation of organic electroluminescent device: the preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing until the pressure is less than 10-5Pa, performing multisource co-evaporation on the anode layer film by using HT-33 as a hole injection material and HT-32 as a doping material, wherein the mass ratio of HT-32 to HT-33 is 1:9, and the film thickness is 10 nm;
evaporating HT-33 as a first hole transport layer of the device on the hole injection layer in vacuum, wherein the film thickness is 40 nm;
evaporating HT-34 on the first hole transport layer in vacuum to be used as a second hole transport layer of the device, wherein the film thickness is 10 nm;
a light-emitting layer of the device is evaporated on the second hole transport layer in vacuum, the light-emitting layer comprises a main material and a dye material, BFH-4 is used as the main material BFD-4 as the dye by a multi-source co-evaporation method, the mass ratio of BFD-4 to BFH-4 is 5:95, and the film thickness is 20 nm;
vacuum evaporating ET-17 on the luminescent layer to be used as a hole blocking layer of the device, wherein the film thickness is 5 nm;
a method of utilizing multi-source co-evaporation on the hole blocking layer, using C1, C5, C6, C10, C18, C130, C143 and C146 comparison materials ET-58 and ET-59 as electron transport materials, Liq as doping materials, the mass ratio of Liq to the used electron transport materials is 1:1, and the film thickness is 23 nm;
liq with a thickness of 1nm was vacuum-evaporated on the Electron Transport Layer (ETL) as an electron injection layer, and an Al layer with a thickness of 80nm as a cathode of the device.
(B) The testing method of the organic electroluminescent device comprises the following steps: the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 5 and comparative examples 1 and 2 were measured at the same luminance using a Photo radiometer model ST-86LA model photoradiometer model PR 750 from Photo Research corporation (photoelectric instrument factory, university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency;
example 1
The compound C1 of the invention is used as an electron transport material, an organic electroluminescent device is prepared according to the preparation process of the organic electroluminescent device, and the device performance test is carried out according to the organic electroluminescent device test method.
Example 2
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C5.
Example 3
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C6.
Example 4
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C10.
Example 5
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C18.
Example 6
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C130.
Example 7
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C143.
Example 8
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with C146.
Example 9
An organic electroluminescent device was produced in the same manner as in example 1, except that Liq was not doped in the electron transport layer.
Example 10
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was used as a hole-blocking layer material in place of ET-17, i.e., C1.
Comparative example 11
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with ET-58.
ET-58 is:
Figure BDA0002378178460000351
comparative example 12
An organic electroluminescent device was produced in the same manner as in example 1, except that compound C1 was replaced with ET-59.
ET-59 is:
Figure BDA0002378178460000352
the organic electroluminescent device properties are given in table 1 below:
table 1:
Figure BDA0002378178460000353
Figure BDA0002378178460000361
in the case of examples 1 to 8 and comparative example 1, in the case where the organic electroluminescent device has the same structure as the organic electroluminescent device, the compound according to the present invention has a significantly reduced voltage and a significantly improved efficiency as compared with the electron transport material ET-58 in comparative example 1 and the electron transport material ET-59 in comparative example 2.
Example 9 shows that the use of the compound of the present invention alone as an electron transporting material without doping Liq results in slightly lower voltage and slightly higher current efficiency than the use of the electron transporting material ET-58 in comparative example 1 and the electron transporting material ET-59 in comparative example 2 with doping Liq, thus showing that the compound of the present invention can achieve satisfactory performance without doping Liq, i.e., with simplified process.
Example 10 shows that the photoelectric properties (voltage and efficiency) of the inventive material are substantially the same when used as both a hole blocking material and an electron transporting material, as compared to ET-17 when used as a hole blocking material and the inventive material is used as an electron transporting material only. Therefore, the preparation process of the device is simplified on the premise of ensuring the photoelectric property.
Compared with comparative example 2, in the case that other materials in the organic electroluminescent device structure are the same, the compound related to the invention has a significantly improved lifetime compared with the electron transport material ET-59 in comparative example 2, which may be due to the influence of the adjustment of the molecular structure on the way of material accumulation and the improvement of stability after device preparation.
The experimental data show that the novel organic material is an organic luminescent functional material with good performance as an electron transport material of an organic electroluminescent device, and is expected to be popularized and applied commercially.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. The various features described in the foregoing detailed description may be combined in any suitable manner without contradiction, and various combinations that are possible in the present invention will not be further described in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A compound having the structure shown in formula (I):
Figure FDA0002378178450000011
in the formula (I), X1～X5Are identical to or different from each other, and X1～X5Each independently represents CR1Or N, and at least one is N, R1Selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 chain alkoxy, substituted or unsubstituted C3-C10 cycloalkoxy, halogen, cyano, nitro, hydroxyl, silaneA group, an amino group and any one of a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamino group, a substituted or unsubstituted C3 to C30 heteroarylamino group, a substituted or unsubstituted C3 to C30 heteroaryl group, and R1May be fused to the attached heteroaromatic ring to form a ring;
in the formula (I), R1 and R2 each represent a single substituent up to the maximum allowable number of substituents, and each is independently selected from any one of hydrogen, a substituted or unsubstituted C1 to C10 chain alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C10 chain alkoxy group, a substituted or unsubstituted C3 to C10 cycloalkoxy group, halogen, cyano, nitro, hydroxyl, silyl, amino, and a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamino group, a substituted or unsubstituted C3 to C30 heteroarylamino group, and a substituted or unsubstituted C3 to C30 heteroaryl group;
in formula (I), Ar is selected from any one of the structures represented by the following formulae (1) to (7):
Figure FDA0002378178450000021
in formulae (1) to (7), X1～X33Are identical to or different from each other, and X1～X33Each independently represents CR2Or N, and X13～X15Not simultaneously being hydrogen, wherein R2Any one selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 chain alkoxy, substituted or unsubstituted C3-C10 cycloalkoxy, halogen, cyano, nitro, hydroxyl, silane, amino and substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, and substituted or unsubstituted C3-C30 heteroaryl;
in formulae (1) to (7), A1～A8The same or different from each other, each independently selected from hydrogen, halogen, cyano, hydroxyl, substituted or unsubstituted amino, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C8932Or any one of unsubstituted C1-C12 alkoxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
in the formulae (1) to (7), n1 to n7 are each independently selected from integers of 0 to 2;
when each of the above groups independently has a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, hydroxyl, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C2-C10 alkenyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl or C6-C30 fused ring heteroaryl.
2. A compound according to claim 1, formula (I), wherein X1～X5At least two of which are N.
3. A compound according to claim 1, formula (I), wherein X3And X4Is N.
4. A compound according to any one of claims 1 to 3, wherein Ar is selected from any one of the structures represented by formula (1), formula (2) or formula (3).
5. A compound according to any one of claims 1 to 3, formula (I), wherein R is1And R2Each independently selected from any one of the following groups:
Figure FDA0002378178450000031
wherein denotes the position of bonding to the attached group, "-" denotes the expression of the ring structure, indicating that the attachment site is located at any position on the ring structure that is capable of bonding.
6. The compound according to claim 1, wherein the compound of formula (I) is selected from the group consisting of:
Figure FDA0002378178450000032
Figure FDA0002378178450000041
Figure FDA0002378178450000051
Figure FDA0002378178450000061
Figure FDA0002378178450000071
Figure FDA0002378178450000081
Figure FDA0002378178450000091
Figure FDA0002378178450000101
Figure FDA0002378178450000111
Figure FDA0002378178450000121
Figure FDA0002378178450000131
Figure FDA0002378178450000141
Figure FDA0002378178450000151
Figure FDA0002378178450000161
Figure FDA0002378178450000171
Figure FDA0002378178450000181
Figure FDA0002378178450000191
Figure FDA0002378178450000201
Figure FDA0002378178450000211
7. use of a compound according to any one of claims 1 to 5 in an organic electroluminescent device, preferably as an electron transport material or a hole blocking material.
8. Use of a compound according to claim 6 in an organic electroluminescent device, preferably as an electron transport material or a hole blocking material.
9. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode, characterized in that the organic layer contains at least one compound according to any one of claims 1 to 6.
10. An organic electroluminescent element comprising a first electrode, a second electrode and an organic layer comprising at least one light-emitting layer between the first electrode and the second electrode, wherein the organic layer further comprises one or more layers selected from the group consisting of an electron-injecting layer, an electron-transporting layer, a hole-injecting layer, a hole-blocking layer and a hole-transporting layer, and wherein the compound according to any one of claims 1 to 6 is contained in the organic layer.
CN202010074641.7A 2020-01-22 2020-01-22 Compound and organic electroluminescent device Pending CN111187201A (en)

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