CN114075131B - TADF material, preparation method thereof and organic electroluminescent device thereof - Google Patents

TADF material, preparation method thereof and organic electroluminescent device thereof Download PDF

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CN114075131B
CN114075131B CN202110008869.0A CN202110008869A CN114075131B CN 114075131 B CN114075131 B CN 114075131B CN 202110008869 A CN202110008869 A CN 202110008869A CN 114075131 B CN114075131 B CN 114075131B
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substituted
group
unsubstituted
tadf
layer
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CN114075131A (en
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马晓宇
李文连
李文军
王聪聪
唐志杰
张宇
陈振生
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to the technical field of luminescent materials, in particular to a TADF material, a preparation method thereof and an organic electroluminescent device thereof. The TADF material is a compound with any one of the following structural formulas or the compoundA tautomer of the compound of the present invention, wherein X ' represents a substitution at any position on the benzene ring, and X ' is C, si or N and when it is N, the corresponding group is not linked, X ' is selected from any one of O, S, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group and a substituted silyl group; r is R 1 ‑R 6 At least one of them is a group represented by the general formula (a),X 1 ‑X 8 are independently selected from C or N, R 21 ‑R 28 Each independently selected from hydrogen, deuterated hydrogen, or a substituent. The TADF material has a suitable triplet energy level and can be used as a sensitizer for the light-emitting layer.

Description

TADF material, preparation method thereof and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a TADF material, a preparation method thereof and an organic electroluminescent device thereof.
Background
The heat-activated delayed fluorescence (TADF) material based on triplet-to-singlet transition found by the Adachi research group of ninety university of japan is a novel material that realizes the reverse intersystem crossing of energy from triplet excited state to singlet excited state by using environmental heat, which can realize high luminous efficiency without using a rare metal of high cost. The TADF material used as the sensitized fluorescent emitter is different from a common fluorescent material and a traditional TADF material, combines the traditional fluorescent material and the TADF material, utilizes the energy collecting capability of the TADF material and the high-purity light color of the traditional fluorescent material, and realizes the preparation of the organic fluorescent OLED with high conversion efficiency, high color purity and low cost. Compared with a pure TADF-luminescent material, the TADF sensitizer material has higher emission efficiency, high singlet energy level and high stability. When a TADF sensitized fluorescent device is adopted and a traditional fluorescent material is used as a light-emitting body, the TADF sensitized fluorescent device is only required to be used as a doping body to be evaporated together with a main material and a fluorescent emitter material to prepare a fluorescent device, then a light-emitting layer is formed, when electron holes are combined into excitons in the main body, the excitons firstly transfer energy to the TADF material, electrons on a triplet state are transferred to the singlet state through the trans-intersystem crossing capability of the TADF material, then the TADF material transfers the singlet state energy to the traditional fluorescent material (called FRET process), and finally fluorescence is emitted by the traditional fluorescent material, and the fluorescence is called super fluorescence. In the whole process, the TADF material is not required to emit light, but rather the material is used for collecting energy and transmitting the energy to the fluorescent emitter material. Because the sensitized fluorescence is emitted by the traditional fluorescent material, the spectrum of the sensitized fluorescent emitter has the advantages of relatively narrow spectrum, long service life and high efficiency of TADF, and is suitable for the OLED display field. Accordingly, there is still a great room for improvement in the above-mentioned requirements of the existing TADF materials, and there is a need in the industry to develop new materials for sensitized fluorescent OLED materials.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a TADF material, a preparation method thereof and an organic electroluminescent device thereof. The TADF material has proper triplet state energy level and can be used as a sensitizer of a luminescent layer, and then energy is effectively transferred to fluorescent molecules to emit light, so that the light emission is realized, the energy collection and the light emission are separated in the process, and the excellent device performance is obtained.
The invention is realized in the following way:
in a first aspect, the present invention provides a TADF material which is a compound having any one of the following structural formulas (1): wherein X ' represents a substitution at any position on the benzene ring, and X ' is C, si or N and when it is N, the corresponding group is not linked, X ' is selected from any one of O, S, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group and a substituted silyl group; r is R 1 -R 6 At least one of them is a group of the formula (a), the remainder R 1 -R 6 Each independently selected from any one of hydrogen, hydroxy, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amino, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amido, substituted or unsubstituted silyl, and substituted or unsubstituted cycloalkyl;
Wherein X is 1 -X 8 Are independently selected from C or N, R 21 -R 28 Each independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted amino, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amido, substituted or unsubstituted silyl, and substituted or unsubstituted cycloalkyl;
and the general formula (a) satisfies at least one of the following conditions: (a) R is R 25 And R is 26 Together form a single bond; (b) R is R 27 And R is 28 Represents the atomic groups required to form together a substituted or unsubstituted benzene ring.
In a second aspect, the present invention provides a method for preparing a TADF material according to any of the preceding embodiments, comprising: selecting any one of the following raw materials of the compound and containing R 1 -R 5 The compound of (2) reacts to obtain the TADF material;
and +.>
Wherein Ra-Re are each independently capable of reacting with the R-containing compounds 1 -R 5 And to obtain the radicals of the TADF material.
In a third aspect, the present invention provides a super luminescent material for preparing a luminescent layer comprising a TADF material according to any of the preceding embodiments;
Preferably, it further comprises a luminescent material;
preferably, it comprises 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material;
more preferably, it comprises, in parts by weight, 20-40 parts of said TADF material, 0.3-5 parts of said luminescent material;
more preferably, it further comprises a host material;
more preferably, the triplet and singlet energy levels of the host material are higher than the triplet and singlet energy levels of the TADF material, respectively, and the triplet and singlet energy levels of the TADF material are higher than the triplet and singlet energy levels of the light-emitting material, respectively.
In a fourth aspect, the present invention provides a transfer material for preparing a transfer layer comprising the TADF material of any of the preceding embodiments;
preferably, it further comprises an electron transport material;
preferably, the lowest unoccupied orbitals of the electron transport material are lower than the lowest unoccupied orbitals of the TADF material;
preferably, the difference in the distance between the lowest unoccupied orbitals of the electron transport material and the lowest unoccupied orbitals of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2eV.
In a sixth aspect, the present invention provides an organic electroluminescent device comprising at least one of the following layered structures:
(1) A light-emitting layer formed of the light-emitting material for producing a light-emitting layer described in the foregoing embodiment;
(2) A transport layer formed of the transport material for preparing a transport layer according to the foregoing embodiment;
preferably, the organic electroluminescent device further comprises a cathode and an anode, and at least one layer of the layered structure of (1) or (2) is disposed between the cathode and the anode.
The invention has the following beneficial effects: (1) According to the TADF material provided by the embodiment of the invention, cyano is taken as an electron-withdrawing group and a group shown in the general formula (a) is taken as an electron-pushing group to act together, so that the charge distribution of the TADF material is regulated, the further delocalization distribution of electrons is facilitated, the singlet state-triplet state energy level of the TADF material is regulated, the RISC rate between energy systems is improved, the reduction of exciton concentration is facilitated, and the service life of a device is prolonged.
(2) The TADF material has proper triplet state energy level, can be used as a sensitizer of a luminescent layer, and can effectively transfer energy to fluorescent molecules to emit light, so that narrow-spectrum light emission is realized, and energy collection and light emission are separated in the process, so that excellent device performance is obtained.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a TADF material (new fluorescent sensitizer is also called auxiliary dopant) which is a compound with any one structural formula in the following general formula (1) or a tautomer thereof,
wherein, X ' represents substitution at any position on the benzene ring, and X ' is C, si or N, and when X ' is N, the corresponding groups are not connected, that is, the connection of each group in the compound provided by the embodiment of the invention is necessarily in accordance with the connection requirement of chemical bonds, such as C bonding 4 bond, O bonding 2 bond and N bonding 3 bond; x' is selected from any one of O, S, substituted or unsubstituted amino, substituted or unsubstituted alkyl and substituted silyl, R 1 -R 6 At least one of them is a group represented by the following general formula (a)>Wherein X is 1 -X 8 Are independently selected from C or N, R 21 -R 28 Each independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted amino, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amido, substituted or unsubstituted silyl, and substituted or unsubstituted cycloalkyl, and the general formula (a) satisfies at least one of the following conditions: (a) R is R 25 And R is 26 Together form a single bond; (b) R is R 27 And R is 28 Represents the atomic groups required to form together a substituted or unsubstituted benzene ring.
Residual R 1 -R 6 Each independently selected from the group consisting of hydrogen, hydroxy, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amino, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amido, substituted or unsubstitutedAny one of unsubstituted silyl groups and substituted or unsubstituted cycloalkyl groups.
Specifically, when R 1 -R 6 When one of them is a group represented by the general formula (a), R 1 -R 3 Any one of the groups is a group shown in a general formula (a); the above R 1 -R 3 Any of the groups of the formula (a) is only one example, R 4 And R is 5 The group of formula (a) may also be selected.
When R is 1 -R 6 When both are groups of the formula (a), R can be selected 1 And R is 3 At the same time, a group of the formula (a), or R 2 And R is 4 And is a group of the general formula (a); r can also be selected 1 And R is 5 At the same time, a group of the formula (a), or R 1 And R is 2 At the same time, a group of the formula (a), or R 2 And R is 5 At the same time, a group of the formula (a), or R 3 And R is 5 And is a group of the general formula (a).
When R is 1 -R 6 When three of them are groups of the formula (a), R may be 1 、R 3 And R is 4 At the same time, a group of the formula (a), or R 1 、R 3 And R is 5 At the same time, a group of the formula (a), or R 2 、R 3 And R is 5 At the same time is a group of the general formula (a) or R 2 、R 3 And R is 4 And is a group of the general formula (a).
Or have R 1 、R 2 、R 3 And R is 4 At the same time is a group of the general formula (a) and R 1 、R 5 、R 3 And R is 4 At the same time, R is a group represented by the general formula (a) 1 -R 6 Four of them are examples of the group of the formula (a), or R 1 -R 6 Are examples of the groups represented by the general formula (a).
The above examples are all R 1 -R 6 At least one of them is an example of a group of the formula (a), when R is not meant 1 -R 6 At least one of the groups of the formula (a) is only exemplified above, other groupsCombinations of the group choices are also within the scope of the embodiments of the present invention.
Further, the group represented by the above general formula (a) is any one of the following groups: substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2,3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl, or substituted or unsubstituted diarylamino; that is to say R 1 -R 5 At least one of them is any one of substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2,3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl, or substituted or unsubstituted diarylamino. Two, three, four or 5 may be selected from any one of the above groups, or a combination of two or more.
More specifically, the group represented by the general formula (a) is any one of the groups represented by the following general formulas:
and +.>Wherein X is 1 -X 8 Are independently selected from C or N, R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 Each independently selected from hydrogen or substituents.
Further, R is as described above 21 -R 28 、R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 Each may be independently selected from any one of hydrogen, deuterated hydrogen, hydroxyl, halogen, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted amino, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amido, substituted or unsubstituted silyl, and substituted or unsubstituted cycloalkyl. Specifically, it may be an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbonAlkylthio of 1 to 20 carbon atoms, alkyl-substituted amino of 1 to 20 carbon atoms, acyl of 2 to 20 carbon atoms, aryl of 6 to 40 carbon atoms, heteroaryl of 3 to 40 carbon atoms, diarylamino of 12 to 40 carbon atoms, substituted or unsubstituted carbazolyl of 12 to 40 carbon atoms, alkenyl of 2 to 10 carbon atoms, alkynyl of 2 to 10 carbon atoms, alkoxycarbonyl of 2 to 10 carbon atoms, alkylsulfonyl of 1 to 10 carbon atoms, haloalkyl of 1 to 10 carbon atoms, amido, alkylamido of 2 to 10 carbon atoms, trialkylsilyl of 3 to 20 carbon atoms, trialkylsilylalkyl of 4 to 20 carbon atoms, trialkylsilylalkenyl of 5 to 20 carbon atoms, trialkylsilylalkynyl of 5 to 20 carbon atoms.
Further preferably, R is as defined above 21 -R 28 、R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 May be independently selected from the group consisting of hydrogen, deuterated hydrogen, hydroxyl, fluorine, chlorine, cyano, nitro, substituted or unsubstituted alkyl of 1 to 10 carbon atoms, substituted or unsubstituted alkoxy of 1 to 10 carbon atoms, substituted or unsubstituted dialkylamino of 1 to 10 carbon atoms, substituted or unsubstituted aryl of 6 to 15 or 6 to 10 carbon atoms, substituted or unsubstituted heteroaryl of 3 to 12 carbon atoms, substituted or unsubstituted diarylamino of 12 to 40 carbon atoms, and substituted or unsubstituted carbazolyl of 12 to 40 carbon atoms.
It should be noted that, R defined above is provided in the embodiment of the present invention 21 -R 28 、R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 The substituent may be an unsubstituted group, may be a further substituted group, and for example, the alkyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms or 1 to 6 carbon atoms may be an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl and n-butyl, or may be an alkyl group substituted with a substituent such as halogen, hydroxyl and nitro. And the alkyl group may be a straight chain or branched alkyl group. For example, the alkoxy group having 1 to 20 or 1 to 10 carbon atoms may be an unsubstituted alkoxy group such as methoxy, ethoxy, propoxy, butoxy, t-butoxy, pentyloxy, hexyloxy, isopropoxy or the like, or may be methoxy, ethoxy or propane substituted with a substituent such as halogen, cyano, hydroxy or nitro Alkoxy substituted with oxy, etc. For example, the alkyl-substituted amine group having 1 to 20 carbon atoms may be CH 3 NH 2 -、(CH 3 ) 2 NH-、C 2 H 5 NH 2 -、(C 2 H 5 ) 2 NH-、C 5 H 12 NH 2 -、(C 5 H 12 ) 2 NH-etc. C n H 2n+1 NH 2 -or (C) n H 2n+1 ) 2 NH-alkyl-substituted amino group having 1 to 20 carbon atoms, wherein n is an integer, or alkyl-substituted amino group having 1 to 20 carbon atoms, in which the alkyl group is further substituted. For example, the acyl group having 2 to 20 carbon atoms may be an acetyl group, a propionyl group, a hexanoyl group or the like. For example, the aryl group having 6 to 40 carbon atoms may be an unsubstituted monocyclic aryl group such as a benzene ring, a benzyl group, an ortho-substituted benzene ring, a meta-substituted benzene ring, a para-substituted benzene ring, a tri-substituted benzene ring or the like (wherein the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group or the like), a condensed unsubstituted aryl group such as anthracene or phenanthrene, a condensed substituted aryl group such as anthracene or phenanthrene after substitution, or a substituted or unsubstituted non-condensed aryl group such as biphenyl or benzophenone group. The alkenyl group having 2 to 10 carbon atoms may be an unsubstituted alkenyl group such as vinyl, propenyl, heptenyl or the like, or a substituted alkenyl group such as halogen, alkyl, nitro or the like. For example, the alkynyl group having 2 to 10 carbon atoms may be an unsubstituted alkynyl group such as an ethynyl group, propynyl group or butynyl group, or an alkynyl group substituted with halogen, alkyl group, nitro group or the like. The heteroaryl group having 3 to 40 carbon atoms may be a substituted or unsubstituted heteroaryl group such as a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a triazolyl group, and a benzotriazole group, and the heteroaryl group may be a group bonded via a heteroatom or may be a group bonded via a carbon atom constituting a heteroaryl ring. For example, the diarylamino group having 12 to 40 carbon atoms may be a tertiary amino group to which two benzene rings are bonded, or a primary amino group to which one benzene ring is bonded, and the benzene ring may be further substituted, and the benzene ring may be replaced with a non-condensed aryl group such as biphenyl or with a condensed aryl group such as anthracene or phenanthrene.
Further, R is as described above 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 The selected groups may be completely different groups, may be partially identical, partially different groups, or may be completely identical groups. For example R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 May all be selected as H or a methyl, ethyl or chlorine atom, or may be R 32 And R is 37 Selected from the same substituent, while the remainder of R in formula (a) 31 、R 33 -R 36 R is as follows 38 All selected from combinations of different groups, R is as defined above 33 And R is 36 Selected from the same substituent, R 34 And R is 35 Selected from the same substituent, R 72 And R is 79 Selected from the same substituent, R 73 And R is 78 Selected from the same substituent, R 74 And R is 77 Selected from the same substituent, and the groups corresponding to the residual R in the general formula (a) are respectively different groups. Similarly, R can also be 72 、R 74 、R 77 And R is 79 Selected from the same substituent, while the remainder of formula (a) are each a combination of different groups, or other R groups also have a partially identical substituent. The above examples are merely illustrative, but are not meant to be limiting.
Preferably, the group of formula (a) is any one of the groups of the following formulae:
and +.>Wherein R is 101 -R 138 、R 141 -R 148 、R 151 -R 162 、R 171 -R 260 R261-R272 and R280-R285 are respectively and independently selected from any one of H, deuterated hydrogen, substituted or unsubstituted alkyl and substituted or unsubstituted aryl; V-V 6 Each independently selected from any one of O, S, substituted or unsubstituted amino, substituted or unsubstituted alkyl and substituted silyl, preferably, under the condition that the chemical bonding relationship is satisfied, any position of the benzene ring in the above general formula may be replaced by N, that is, the position of the benzene ring condensed with other rings cannot be N, and the other positions are replaced by N, so that the corresponding group cannot be connected.
The above-mentioned substituted or unsubstituted alkyl group may be selected from the above-mentioned R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 The alkyl group defined in (a) may be an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl or n-butyl, or an alkyl group substituted with a substituent such as halogen, hydroxy or nitro. And the alkyl group may be a straight chain or branched alkyl group. The substituted or unsubstituted aromatic group may be selected from the group consisting of R 31 -R 38 、R 41 -R 46 、R 51 -R 62 And R is 71 -R 80 Examples of the aryl group defined in (a) may be an unsubstituted monocyclic aryl group such as a benzene ring, an ortho-substituted benzene ring, an meta-substituted benzene ring, a para-substituted benzene ring, a homotrisubstituted benzene ring or the like (wherein the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group or the like), a condensed unsubstituted aryl group such as anthracene or phenanthrene, a condensed substituted aryl group such as substituted anthracene or phenanthrene, or a substituted or unsubstituted non-condensed aryl group such as biphenyl or benzophenone group. The above-mentioned substituted or unsubstituted amine groups may be selected from CH 3 NH 2 -、(CH 3 ) 2 NH-、C 2 H 5 NH 2 -、(C 2 H 5 ) 2 NH-、C 5 H 12 NH 2 -、(C 5 H 12 ) 2 NH-etc. C n H 2n+1 NH 2 -or (C) n H 2n+1 ) 2 NH-carbon number 1-20, wherein n is an integer, or an alkyl-substituted amino group having 1 to 20 carbon atoms in which the alkyl group is further substituted; or two tertiary amine groups connected with benzene rings or one primary amine group connected with benzene rings, wherein the benzene rings can be further substituted, and the benzene rings can be replaced by non-condensed aryl groups such as biphenyl or condensed aryl groups such as anthracene and phenanthrene. Substituted silyl groups may be selected from-Si (Me) 3 、(C 2 H 5 ) 3 Si-、(C 5 H 12 ) 3 Si-etc. (C) n H 2n+1 ) 3 Si-, n is an integer, and the above alkyl group may be a further substituted alkyl group.
More specifically, the group represented by the general formula (a) is any one of the groups represented by the following general formulae (1 d) to (44 d):
and +.>Wherein X is independently selected from any one of O, S, substituted or unsubstituted amino, substituted or unsubstituted alkyl and substituted silyl, and X 1 -X 8 Each independently selected from C or N; and hydrogen in the benzene ring in the group represented by any of the general formulae (1 d) to (44 d) is replaced with deuterium atom; preferably, the benzene ring in the group represented by any of the general formulae (1 d) to (44 d) may be bonded with a substituent selected from any of hydrogen, deuterated hydrogen, hydroxy, halogen, cyano, C1-C6 alkyl and C6-C10 aryl One of the two; the substituent is preferably R100; preferably, under the condition that the chemical bonding relation is satisfied, any position of the benzene ring in the general formula can be replaced by N, that is, the position condensed with other rings in the benzene ring cannot be N, and the other positions are replaced by N, and the corresponding groups cannot be connected.
The above-mentioned ribbon-like keys indicate the positions of the connection keys.
The above is for R 1 -R 6 At least one of them is a group of the formula (a), and the remainder of R is as follows 1 -R 6 Description will be made. The method comprises the following steps: residual R 1 -R 6 Each independently selected from any of hydrogen, hydroxy, halogen, cyano, nitro, C1-C20 substituted or unsubstituted saturated alkyl, C2-C10 substituted or unsubstituted alkenyl, C2-C10 substituted or unsubstituted alkynyl, C6-C40 substituted or unsubstituted non-heteroaryl, C3-C40 substituted or unsubstituted heteroaryl, C1-C20 substituted or unsubstituted alkoxy, C1-C20 substituted or unsubstituted alkylthio, -NH-, C1-C20 substituted amino, C2-C20 substituted or unsubstituted acyl, sulfonyl, C1-C10 alkyl substituted sulfonyl, amido, C1-C10 alkyl substituted amido, C2-C10 alkyl substituted ester, C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl, C5-C20 trialkylsilylalkynyl, and C3-C20 substituted or unsubstituted cycloalkyl. Further preferably, the remaining R1-R5 are each independently selected from the group consisting of hydrogen, hydroxy, halogen, cyano, nitro, C1-C6 saturated alkyl, C3-C10 unsubstituted cycloalkyl, C6-C20 unsubstituted fused cycloalkyl, C6-C20 substituted non-fused and non-heteroaromatic group, C10-C40 substituted fused non-heteroaromatic group, C1-C10 alkyl substituted alkoxy, C1-C10 alkyl substituted alkylthio, -NH-, C1-C10 alkyl substituted amino, C6-C20 aryl substituted amino, acyl, sulfonyl, C2-C10 alkanoyl, C6-C20 aryl substituted acyl, C1-C10 alkyl substituted sulfonyl, amido, C2-C8 alkyl substituted ester group, C3-C15 trialkylsilyl, C4-C15 trialkylsilylalkyl, C5-C15 trialkylsilylalkenyl, C5-C15 trialkylsilylalkyl and C3-C15 alkynyl or substituted alkynyl Unsubstituted cycloalkyl groups. Residual R 1 -R 5 Each independently selected from any one of hydrogen, cyano, carbazolyl, diarylamino, C3-C10 alkoxy, C1-C6 alkyl, and C6-C10 aryl.
It should be noted that the embodiment of the present invention provides the remaining R defined above 1 -R 6 The alkyl group having 1 to 20 or 1 to 6 carbon atoms may be an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl or n-butyl, or an alkyl group substituted with a substituent such as halogen, hydroxy or nitro. And the alkyl group may be a straight chain or branched alkyl group. For example, the alkenyl group having 2 to 10 carbon atoms may be an unsubstituted alkenyl group such as vinyl, propenyl, heptenyl or the like, or a substituted alkenyl group such as halogen, alkyl, nitro or the like. For example, the alkynyl group having 2 to 10 carbon atoms may be an unsubstituted alkynyl group such as an ethynyl group, propynyl group or butynyl group, or an alkynyl group substituted with halogen, alkyl group, nitro group or the like. The heteroaryl group having 6 to 40 carbon atoms may be a substituted or unsubstituted heteroaryl group such as a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a triazolyl group, a piperazinyl group, or a benzotriazole group, and the heteroaryl group may be a group bonded via a heteroatom or may be a group bonded via a carbon atom constituting a heteroaryl ring. For example, the aryl group having 6 to 40 carbon atoms may be an unsubstituted monocyclic aryl group such as a benzene ring, a benzyl group, an ortho-substituted benzene ring, a meta-substituted benzene ring, a para-substituted benzene ring, a tri-substituted benzene ring or the like (wherein the substituted group may be a halogen, an alkyl group, a nitro group, a cyano group or the like), a condensed unsubstituted aryl group such as anthracene or phenanthrene, a condensed substituted aryl group such as anthracene or phenanthrene after substitution, or a substituted or unsubstituted non-condensed aryl group such as biphenyl or benzophenone group. For example, the alkoxy group having 1 to 20 or 1 to 10 carbon atoms may be an unsubstituted alkoxy group such as methoxy, ethoxy, propoxy, butoxy, t-butoxy, pentoxy, hexoxy, isopropoxy or the like, or a substituted alkoxy group such as methoxy, ethoxy, propoxy or the like substituted with a substituent such as halogen, cyano, hydroxy, nitro or the like. For example, the alkyl-substituted amine group having 1 to 20 carbon atoms may be CH 3 NH 2 -、(CH 3 ) 2 NH-、C 2 H 5 NH 2 -、(C 2 H 5 ) 2 NH-、C 5 H 12 NH 2 -、(C 5 H 12 ) 2 NH-etc. C n H 2n+ 1 NH 2 -or (C) n H 2n+1 ) 2 NH-alkyl-substituted amino having 1 to 20 carbon atoms, wherein n is an integer, or alkyl-substituted amino having 1 to 20 carbon atoms, in which the alkyl group is further substituted. For example, the aryl-substituted amine group having 6 to 20 carbon atoms may be a tertiary amine group in which two benzene rings are linked, or a primary amine group in which one benzene ring is linked, and the benzene ring may be further substituted, and the benzene ring may be replaced with a non-condensed aryl group such as biphenyl or a condensed aryl group such as anthracene or phenanthrene. For example, the alkyl acyl group having 2 to 20 carbon atoms may be an acetyl group, a propionyl group, a hexanoyl group or the like. For example, the C6-C20 aromatic group-substituted acyl group may be an aromatic group-substituted acyl group such as an acetyl group substituted with a benzene ring or an acetyl group substituted with a substituted benzene ring. C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl and C5-C20 trialkylsilylalkynyl groups may be selected from-Si (Me) 3 、(C 2 H 5 ) 3 Si-、(C 5 H 12 ) 3 Si-etc. (C) n H 2n+1 ) 3 Si-silane groups, n being an integer, or-Si (Me) 2 C 2 H 5 、Me(C 2 H 5 ) 2 Si-or the like; or Me (C) 2 H 3 ) 2 Si-etc. C n H 2n+12 (C n H 2n-1 ) 2 Si-or the like, or Me 2 C 2 H 3 Si-etc. (C) n H 2n+1 ) 2 (C n H 2n-1 ) Si-or the like, or Me 2 C 2 HSi-et al (C) n H 2n+1 ) 2 (C n H 2n-3 ) Si-or the like, or Me (C) 2 H) 2 Si-etc. C n H 2n+1 (C n H 2n-3 ) 2 Si-, etc. n is an integer, and preferably n is 3 to 10, and the above alkyl group may be a further substituted alkyl group.
Further, the remainder R 1 -R 6 Are independently selected from hydrogen and hydroxyAny one of halogen, cyano, nitro, substituted or unsubstituted 9-carbazolyl, substituted or unsubstituted 1,2,3, 4-tetrahydro-9-carbazolyl, substituted or unsubstituted 1-indolyl, substituted or unsubstituted diarylamino, and a group represented by R100 of the following structural formula,
in particular, when X 1 -X 8 When both are C, the rest R 1 -R 6 Each independently selected from the group consisting of hydroxy, halogen, cyano, nitro, substituted or unsubstituted alkanyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted ester, substituted or unsubstituted amine, substituted or unsubstituted acyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted amide, substituted or unsubstituted silane, and substituted or unsubstituted cycloalkyl, and any of the following R100 groups:
the remainder R 1 -R 6 May be the same group, or may be selected from completely different groups, or may be partially the same group, partially different groups, e.g. the remainder R 1 -R 5 One of which is cyano, one of which is hydroxy or halogen atom, the last remaining R 1 -R 6 Is a substituted or unsubstituted 9-carbazolyl group, then R is the remainder 1 -R 6 All of which are different groups, although other groups may be used, or the same group, or part of the groups may be the same. Embodiments of the present invention will not be described in detail.
Further, X' is selected from any one of O, S, -NH-, C1-C20 substituted amino, substituted or unsubstituted saturated alkyl and substituted silyl; preferably, X' is selected from O, S, -NH-, C1-C20 substituted amine groups, C1-C10 unsubstituted saturated alkyl groups, C3-C20 trialkylsilyl groups, C4-C20Any one of trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl and C5-C20 trialkylsilylalkynyl; preferably, X' is selected from O, S, -NH-, - (Me) 2 and-Si (Me) 3 Any one of the following.
It is noted that the substituted amine group may be CH 3 NH 2 -、(CH 3 ) 2 NH-、C 2 H 5 NH 2 -、(C 2 H 5 ) 2 NH-、C 5 H 12 NH 2 -、(C 5 H 12 ) 2 NH-etc. C n H 2n+1 NH 2 -or (C) n H 2n+1 ) 2 NH-alkyl substituted amino with 1-20 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, or n-butyl, or an alkyl group substituted with a substituent such as halogen, hydroxy, or nitro. And the alkyl group may be a straight chain or branched alkyl group. C3-C20 trialkylsilyl, C4-C20 trialkylsilylalkyl, C5-C20 trialkylsilylalkenyl and C5-C20 trialkylsilylalkynyl groups may be selected from-Si (Me) 3 、(C 2 H 5 ) 3 Si-、(C 5 H 12 ) 3 Si-etc. (C) n H 2n+1 ) 3 Si-silane groups, n being an integer, or-Si (Me) 2 C 2 H 5 、Me(C 2 H 5 ) 2 Si-or the like; or Me (C) 2 H 3 ) 2 Si-etc. C n H 2n+12 (C n H 2n-1 ) 2 Si-or the like, or Me 2 C 2 H 3 Si-etc. (C) n H 2n+1 ) 2 (C n H 2n-1 ) Si-or the like, or Me 2 C 2 HSi-et al (C) n H 2n+1 ) 2 (C n H 2n-3 ) Si-or the like, or Me (C) 2 H) 2 Si-etc. C n H 2n+1 (C n H 2n-3 ) 2 Si-, etc. n is an integer, and preferably n is 3 to 10, and the above alkyl group may be a further substituted alkyl group.
Embodiments of the invention alsoA preparation method of the TADF material is provided, which comprises the steps of selecting any one of the following compounds and containing R 1 -R 6 The compound of (2) reacts to obtain the TADF material;
and +.>
Wherein Ra-Re are each independently capable of reacting with the R-containing compounds 1 -R 5 And to obtain the radicals of the TADF material. Specifically, the compound raw material is any compound shown in the general formula (A), at least 2 of Ra-Re are halogen, at least one is any one selected from borate, pinacol borate and pinacol borate derivative groups, the rest is H, and the halogen, the borate, the pinacol borate and the pinacol borate derivative groups in the raw material are all needed to exist, so that subsequent reaction can be carried out.
Comprising the following steps: the compound starting material is reacted with R100-halogen such that borate, pinacol borate and pinacol borate derivative groups react with halogen to form intermediate 1 comprising R100, and intermediate 1 is then reacted with a starting material comprising formula (a) to form the TADF material. In forming intermediate 1, only the borate, pinacol borate, and pinacol borate derivative groups are reacted with halogen to graft R100, while the other groups in the starting materials are not involved in the reaction. When the intermediate 1 is reacted with a raw material containing a raw material of the general formula (a), only halogen groups of the intermediate 1 react with the raw material containing the general formula (a), and then the general formula (a) is grafted to form the TADF material.
R100 corresponds to the remainder R 1 -R 6 That is, the starting R100-halogen may be a halogen containing the remainder of R 1 -R 6 Radicals (C)The halogen in the starting material then reacts with the borate, pinacol borate and pinacol borate derivative to form the remaining R 1 -R 6 Intermediate 1 of the group and then intermediate 1 is reacted with a starting material comprising formula (a) to form the TADF material.
For example, the present invention exemplifies the following synthetic routes:
and
or the preparation method can be as follows: the compound raw material is any compound shown in the general formula (A), at least 3 of Ra-Re are halogen, and the activity difference exists among 3 halogens, R100-amino with higher activity in the compound raw material reacts to form an intermediate 1 containing R100, and then the intermediate 1 reacts with the raw material containing the general formula (a) to form the TADF material. In the process of forming the intermediate 1, the amino group in the R100-amino group reacts with halogen with higher activity in the raw material of the compound, while the halogen with other active bases does not react. While intermediate 1 reacts with a starting material comprising a starting material of formula (a), only the remaining less reactive halogen groups of intermediate 1 react with the starting material comprising formula (a), followed by grafting onto formula (a) to form the TADF material.
For example, the present invention exemplifies the following synthetic routes:
the embodiment of the invention provides a super fluorescent material for preparing a light-emitting layer, wherein the light-emitting layer can be a single-color light-emitting layer emitting red, green, blue and the like. The plurality of monochromatic light emitting layers with different colors can be arranged in a plane according to the pixel pattern, or can be stacked together to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light emitting layer may be a single color light emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
The super fluorescent material comprises the TADF material; further, it also comprises a luminescent material. Preferably, it comprises 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material; more preferably, it comprises 20 to 40 parts by weight of the TADF material, 0.3 to 5 parts by weight of the luminescent material. The super fluorescent material prepared by adopting the proportion can ensure that the formed luminescent material has good performance, so that the luminescent layer formed by the super fluorescent material has good performance.
More preferably, it further comprises a host material; and the triplet and singlet energy levels of the host material are higher than the triplet and singlet energy levels of the TADF material, respectively, and the triplet and singlet energy levels of the TADF material are higher than the triplet and singlet energy levels of the light-emitting material, respectively. The main body material and the luminescent material with the specifications can be favorable for matching the main body material, the luminescent material and the TADF material, and then the performance of the luminescent layer can be improved.
Specifically, the host material may be selected from those which can be used in combination with a fluorescent electroluminescent material, a phosphorescent electroluminescent material, a thermally activated delayed fluorescent luminescent material, or the like in the prior art, and other host materials may be selected, for example, those described in advanced materials, 2017, 29, 1605444, journal of Material chemistry, journal of Material Chemistry C, 2016,4, 11355-11381, chemical Science, 2016,7, 3355-3363, solid Films, 2016, 619, 120-124, or the like. Further, since the TADF organic EL element requires high T1 energy in the host material of the light-emitting layer, the host material for the phosphorescent organic EL element described in "chemical society review (Chemistry SocietyReviews)", 2011, 40, 2943-2970 can be used as the host material for the TADF organic EL element. Alternatively, the host material may be selected from at least one of the compounds shown below as TDH 1-TDH 58:
or further, the host material is a compound having at least one structure selected from the group of partial structures (H-a) represented by the following formula, and at least one hydrogen atom in each structure in the group of partial structures (H-a) may be substituted by any one structure in the group of partial structures (H-a) or the group of partial structures (H-B), and at least one hydrogen in these structures may be substituted by heavy hydrogen, halogen, cyano, alkyl group having 1 to 4 carbon atoms (e.g., methyl or tert-butyl), trimethylsilyl group, or phenyl group. The host material is preferably a compound having one to three structures selected from the group of partial structures (H-a) and one structure selected from the group of partial structures (H-B), and more preferably a compound having a carbazolyl group as the group of partial structures (H-a).
Further, the luminescent material may include, but is not limited to, a combination of one or more of the following FD1-FD 93.
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Further toThe luminescent material may also be selected from one or more of the following combinations of TDE-1-TDE-39: />
It should be noted that the above-mentioned host materials and luminescent materials of the luminescent layer are merely examples, and it is not meant that the host materials and luminescent materials of the luminescent layer according to the embodiments of the present invention can only use the above materials or combinations thereof, and the host materials and luminescent materials of the luminescent layer that can satisfy the requirements in the prior art are also within the scope of the embodiments of the present invention.
Further, the TADF material provided by the embodiment of the present invention may also be used for preparing a transport layer, so that the embodiment of the present invention further provides a transport material for preparing a transport layer, which includes the TADF material described above; the device further comprises an electron transport material. I.e. the TADF material can be used for the preparation of electron transport layers; it is also required that the lowest unoccupied orbitals of the electron transport material be lower than the lowest unoccupied orbitals of the TADF material; preferably, the difference in the distance between the lowest unoccupied orbitals of the electron transport material and the lowest unoccupied orbitals of the TADF material is less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2eV. The electron transport material and the TADF material can ensure that the electron transport material has good electron transport effect.
In particular, the electron transport material may be selected from one or a combination of more of the following compositions ET-1 to ET-57,
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it should be noted that the above-mentioned electron transport materials are only examples, and it is not meant that the electron transport materials according to the embodiments of the present invention can only use the above materials or combinations thereof, and the electron transport materials that can meet the requirements in the prior art are also within the scope of the embodiments of the present invention.
Further, the transport layer provided by the embodiment of the invention further comprises a hole transport layer, and the transport material further comprises a hole transport material; in this case, the TADF material may also be used in the preparation of the hole transport layer. The highest occupied orbitals of the hole transport material are required to be higher than the highest occupied orbitals of the TADF material, preferably the highest occupied orbitals of the hole transport material differ from the highest occupied orbitals of the TADF material by less than 0.5eV, preferably less than 0.3eV, more preferably less than 0.2eV. The performance of the hole transport material can be ensured by adopting the hole transport material.
Specifically, the hole transport material may be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers, or conductive dopant-containing polymers such as polystyrene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives, or any one of or any combination of the following compounds shown by HT-1 to HT-34:
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That is, the TADF material described above can be used to prepare an electron transport layer and a hole transport layer, respectively.
Further, an embodiment of the present invention also provides an electromechanical device, which includes at least one of the following layered structures:
(1) A light-emitting layer formed of the light-emitting material for producing a light-emitting layer described in the foregoing embodiment;
(2) The transport layer formed of the transport material for preparing the transport layer according to the foregoing embodiment.
The organic electroluminescent device may be an Organic Light Emitting Diode (OLED), a light emitting electrochemical cell, an OLED sensor, in particular an organic light emitting diode, an organic solar cell, an organic transistor, an organic field effect transistor, an organic laser and a down conversion element.
The embodiment of the invention is described by taking an OLED as an example:
the organic electroluminescent device further includes a cathode and an anode, i.e., a first electrode and a second electrode, wherein a substrate may be used under the first electrode or over the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. A Thin Film Transistor (TFT) may be provided on a substrate for a display.
Further, the first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as the anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), or the like, and any combination thereof may be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.
At least one layer of the layered structure described in (1) to (3) above is provided between the cathode and the anode. And the layered structure is formed on the electrode by vacuum thermal evaporation, spin coating, printing and the like.
Further, the organic electroluminescent device further includes a hole transport region, which is located between the anode and the light emitting layer, and the hole transport region may be a Hole Transport Layer (HTL) having a single layer structure, and the HTL may be an HTL provided by the embodiment of the present invention or an HTL formed of a hole transport material in the prior art. The hole transport region may have a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
Wherein the hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more of the compounds HT-1 through HT-34 described above, or one or more of the compounds HI1 through HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1 to HI3 described below.
The light-emitting layer may be the light-emitting layer provided by the above embodiment of the present invention, or may be a light-emitting layer formed of a light-emitting material of the prior art. And in an OLED device, a single light emitting technology may be used, or a combination of multiple different light emitting technologies may be used. The different luminescent materials classified by the technology can emit light of the same color, and can also emit light of different colors.
Further, the organic electroluminescent device further includes an electron transport region, which may be an Electron Transport Layer (ETL) of a single layer structure, between the light emitting layer and the cathode, and may be a multi-layer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL). The electron transport layer can be the electron transport layer provided by the embodiment of the invention, and can also be an electron transport layer material formed by the electron transport material disclosed in the prior art.
An electron injection layer may also be included in the OLED device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following: liQ, liF, naCl, csF Li 2 O，Cs 2 CO 3 BaO, na, li and Ca。
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment of the invention provides a TADF material (with the number of TDS-007), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
the specific process is as follows:
bromo-tert-butane (1.00 eq), 3, 5-difluoro-4-cyanophenylboronic acid (1.80 eq), pd under nitrogen 2 (dpa) 3 (0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100℃for 16 hours. The reaction mixture was then added to 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2×300 mL), the organic phases were combined, the solvent was removed by rotary evaporation, the salts were removed by washing with water after suction filtration, the cake was dried, and column chromatography (eluent: ethyl acetate: petroleum ether=1:8) gave the intermediate as a solid, according to the invention the corresponding borate ester could be used instead of boric acid.
Carbazole (2.40 eq) and the above synthesized intermediate (1.00 eq) were added under nitrogen to a two-necked round bottom flask equipped with reflux condenser, cesium carbonate (4 eq) was added, and DMF (10 eq) was added to form a suspension, which was stirred at room temperature for 30min. TDS-007 (1.00 eq.) was poured all at once into the reaction and stirred at 155℃for 12 hours. Washing twice with saturated sodium chloride solution, washing twice with Na 2 SO 4 Drying, removing the solvent, and finally, recrystallizing in toluene or by 14 dichloromethane/petroleum ether purification of the crude product, the product was obtained as a solid. The actual measurement data of the mass spectrum is 489.25.
Example 2
The embodiment of the invention provides a TADF material (with the number of TDS-022), which has the structural formula shown as follows:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
the specific process is as follows:
bromoadamantane (1.00 eq), 3, 5-difluoro-4-cyanophenylboronic acid (1.80 eq), pd under nitrogen 2 (dpa) 3 (0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100℃for 16 hours. The reaction mixture was then added to 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2X 300 mL), the solvent was removed by rotary evaporation, and after suction filtration it was washed with water
Salts were eluted with ethanol, the filter cake was dried, and column chromatography (eluent: ethyl acetate: petroleum ether=1:8) to give the intermediate as a solid, according to the invention the corresponding borate ester could be used instead of boric acid.
3, 6-Di-tert-butyl-9 h-pyrido [2,3-b ] under nitrogen]Indole (2.40 eq) and the previously synthesized intermediate (1.00 eq) were added to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00 mmol) and DMF (100 mL) were added to form a suspension which was stirred at room temperature for 30min. TDS-022 (1.00 eq.) was poured all at once into the reaction solution and stirred for 12 hours at 155 ℃. Washing twice with saturated sodium chloride solution, washing twice with Na 2 SO 4 Drying, removing solvent, and mostAfter this time, the crude product was obtained as a solid by recrystallisation from toluene or purification from 1:4 methylene chloride/petroleum ether, and the actual mass spectrum was 791.60.
Example 3
The embodiment of the invention provides a TADF material (with the number of TDS-040), which has the structural formula as follows:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
the specific process is as follows:
diphenylamine (1.00 eq), 4-bromo-2, 6-difluorobenzonitrile (1.60 eq), tetraphenylphosphine palladium (0.002 eq) and potassium carbonate (2 eq) are added into a three-necked flask which is replaced three times by nitrogen, and the mixture is added into a mixed solvent of toluene, ethanol and water (180 mL;60 mL) respectively, the temperature is raised to 110 ℃ for reflux reaction for 8 hours, after the reaction is finished, the mixture is cooled to room temperature, after the solid precipitation is finished, the mixture is filtered by suction, and then washed by water to remove salt, the filter cake is leached by ethanol, and column chromatography (eluent: ethyl acetate: petroleum ether=1:8) is carried out to obtain a solid product.
Carbazole (2.40 eq) and the above synthesized intermediate (1.00 eq) were added under nitrogen to a two-necked round bottom flask equipped with reflux condenser. Cesium carbonate (40.00 mmol) and DMF (100 mL) were added to form a suspension which was stirred at room temperature for 30min. TDS-108 (1.00 eq.) was poured all at once into the reaction and stirred at 155℃for 12 hours. The crude product was obtained as a solid by washing twice with saturated sodium chloride solution, drying over Na2SO4, removing the solvent, and finally purifying the crude product by recrystallisation in toluene or by 1:4 dichloromethane/petroleum ether. The actual mass spectrum measurement was 600.30.
Example 4
The embodiment of the invention provides a TADF material (with the number of TDS-108), which has the structural formula as follows:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
the specific process is as follows:
3, 5-difluoro-4-cyanophenylboronic acid (1.00 eq), bromo-tert-butane (1.80 eq), pd under nitrogen 2 (dpa) 3 (0.02 eq), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos) (0.08 eq) and tripotassium phosphate (3.00 eq) were stirred under nitrogen in a toluene/water mixture (ratio 6:1) at 100℃for 16 hours. The reaction mixture was then added to 600mL of saturated sodium chloride solution and extracted with ethyl acetate (2×300 mL), the solvent was removed by rotary evaporation, the salt was removed by washing with water after suction filtration, the cake was dried by rinsing with ethanol, column chromatography (eluent: ethyl acetate: petroleum ether=1:8) to give the intermediate as a solid, according to the invention the corresponding borate ester may be used instead of boric acid.
Under nitrogen, 12-dimethyl-5, 12-dihydro-indeno [1,2-c ]]Carbazole (2.40 eq) and the above synthesized intermediate (1.00 eq) were added to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00 mmol) and DMF (100 mL) were added to form a suspension which was stirred at room temperature for 30min. TDS-108 (1.00 eq.) was poured all at once into the reaction and stirred at 155℃for 12 hours. Washing twice with saturated sodium chloride solution, washing twice with Na 2 SO 4 The crude product was dried above, the solvent removed, and finally, the product was obtained as a solid by recrystallisation from toluene or purification from 1:4 methylene chloride/petroleum ether. The actual measurement of mass spectrum is: 721.38.
example 5
The embodiment of the invention provides a TADF material (with the number of TDS-117), which has the following structural formula:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
the specific process is as follows:
deuterated carbazole (2.40 eq) was added under nitrogen to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00 mmol) and DMF (100 mL) were added to form a suspension which was stirred at room temperature for 30min. 3, 5-difluorobenzonitrile (1.00 eq.) was poured all at once into the reaction solution and stirred at 155℃for 12 hours. Washing twice with saturated sodium chloride solution, washing twice with Na 2 SO 4 The crude product was dried above, the solvent removed, and finally, the product was obtained as a solid by recrystallisation from toluene or purification from 1:4 methylene chloride/petroleum ether. The actual mass spectrum measurement was 449.31.
Example 6
The embodiment of the invention provides a TADF material (with the number of TDS-123), which has the structural formula as follows:
the embodiment of the invention provides a preparation method of a TADF material, which is synthesized by referring to the following synthesis paths:
The specific process is as follows:
nitrogen bar3, 6-dimethoxy-9 h-carbazole (2.40 eq) was added under part to a two-necked round bottom flask equipped with a reflux condenser. Cesium carbonate (40.00 mmol) and DMF (100 mL) were added to form a suspension which was stirred at room temperature for 30min. 2, 4-Dibromothiophene-3-carbonitrile (1.00 eq.) was poured into the reaction solution all at once and stirred at 155℃for 12 hours. Washing twice with saturated sodium chloride solution, washing twice with Na 2 SO 4 The crude product was dried above, the solvent removed, and finally, the product was obtained as a solid by recrystallisation from toluene or purification from 1:4 methylene chloride/petroleum ether. The actual mass spectrum measurement was 559.20.
Other examples of TADF Material
The invention refers to the preparation method to prepare the compound shown in the following structural formula, and the compound is characterized by mass spectrum, and the result is shown in the following table:
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verification example
In order to verify that the TADF material provided by the embodiment of the invention can be used for an organic electroluminescent device (OLED), the verification example provides a preparation process of the OLED:
transparent glass with ITO on the surface was used as a substrate, and then each was ultrasonically cleaned with deionized water, acetone, and ethanol for 15 minutes, respectively, and then treated in a plasma cleaner for 2 minutes.
Placing the above glass substrate with anode in vacuum chamber, and vacuumizing to 4×10 -5 Pa, the deposition rate of the organic layer and the aluminum layer is 0.1-0.2 nm/s, and the deposition rate of the LiF layer is 0.01nm/s, and the specific steps are as follows: at a vacuum degree of 2X 10 -4 Under the condition that HT-8 described above is used as a hole injection layer on the anode layer film by vacuum evaporation, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 40nm;
vacuum evaporating HI-3 as the hole injection layer of the device on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 5nm;
vacuum evaporating HT-32 as hole transport layer of the device above the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 45nm;
vacuum vapor-depositing HT-14 described above as the hole transport layer of the device on the hole transport layer at a vapor deposition rate of 0.1nm/s and a total vapor deposition film thickness of 10nm;
the luminescent layer of the vacuum evaporation device is arranged on the hole transmission layer, the luminescent layer comprises a main material, a TADF material and a luminescent material, the main material is regulated to be TDH-1 to TDH-58 recorded in the specification, the evaporation rate is 0.1 to 0.2nm/s, the TADF material TDS-001 to TDS-133 provided by the embodiment of the invention, the luminescent material is FD-1 to FD-93 recorded in the specification, the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 25nm;
Vacuum evaporating electron transport layer material ET-63 of the device on the luminescent layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 5nm;
and vacuum evaporation is carried out on an Electron Transport Layer (ETL) to form an ET-59+Liq layer with the thickness of 25nm as the electron transport layer, wherein the weight ratio of the ET-59 to the LiQ layer is 1:1, and LiF with the thickness of 1nm and an Al layer with the thickness of 100nm are vacuum evaporation on the electron transport layer to form the cathode of the device.
Wherein, the structural formulas of the comparison compounds used in the above HT-8, HI-3, HT-32, HT-14, ET-63, ET-59, liq and the subsequent verification of comparative example 3 are as follows:
(comparative Compound)
The verification of a specific OLED obtained is for example as follows:
verification example 1:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% TAS-007:1% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-007 material provided in synthetic example 1, wherein the TDS-007 material comprises 30% of the total mass and the FD-9 material comprises 1% of the total mass.
Verification example 2:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% TDS-007:1% FD-72 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is TDS-007 provided in Synthesis example 1, wherein the luminescent material TDS-007 material comprises 30% of the total mass and the luminescent material FD-72 comprises 1% of the total mass.
Verification example 3:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:29% TAS-007:2% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the TDS-007 material comprises 20% of the total mass and the FD-9 material comprises 2% of the total mass.
Verification example 4:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% TDS-022:2% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-022 material provided in synthetic example 2, wherein the luminescent material TDS-022 material accounts for 25% of the total mass, and the luminescent material FD-9 accounts for 2% of the total mass.
Verification example 5:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% TDS-108:1% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-108 material provided in synthetic example 4, wherein the luminescent material TDS-108 material accounts for 30 percent of the total mass and the luminescent material FD-9 accounts for 1 percent of the total mass.
Verification example 6:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% TDS-117:1% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-117 material provided in synthetic example 5, wherein the luminescent material TDS-117 material accounts for 30% of the total mass and the luminescent material FD-9 accounts for 1% of the total mass.
Verification example 7:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:28% TDS-117:3% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TADF material provided in synthetic example 5, wherein the luminescent material TDS-117 material accounts for 40 percent of the total mass and the luminescent material FD-9 accounts for 3 percent of the total mass.
Verification example 8:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:28% TDS-123:3% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TADF material provided in synthetic example 6, wherein the luminescent material TDS-123 material accounts for 35 percent of the total mass and the luminescent material FD-9 accounts for 5 percent of the total mass.
Verification example 9:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:28% TDS-007:4% FD-72 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is TDS-007 provided by Synthesis example 1, wherein the luminescent material TDS-007 material comprises 30% of the total mass and the luminescent material FD-72 comprises 0.3% of the total mass.
Verification examples 10 to 23:
the TDS-007 in the verification example 1 was replaced with TDS-008, TDS-009, TDS-016, TDS-017, TDS-021, TDS-024, TDS-040, TDS-118 and TDS-119 in this order to obtain verification examples 10 to 18.
The TDS-007 in the above-mentioned verification example 2 was replaced with TDS-008 and TDS-118 in this order to obtain verification examples 19 and 20. Comparative example was verified:
a verification comparative example was prepared with reference to the above verification example, which is different from the verification example in that a TADF material was not used or a TADF material was directly used or a light-emitting material was used or a transmission material was different, specifically as follows:
comparative example 1 was verified:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:1% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), the comparative verification example differs from verification example 1 in that: the light emitting layer was not added with the TADF material of example 1.
Comparative example 2 was verified:
ITO (150 nm)/HT-8 (40 nm)/HI-3 (5 nm)/HT-32 (45 nm)/HT-14 (10 nm)/TDH-14:30% contrast compound: 1% FD-9 (25 nm)/ET-63 (5 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material contrast compound comprises 30% of the total mass and the luminescent material FD-9 comprises 1% of the total mass.
Comparative example 3 was verified:
ITO (150 nm)/HI-3 (5 nm)/HT-14 (10 nm)/TDH-14:30% TAS-001:1% FD-9 (25 nm)/(ET-59+LiQ) (25 nm)/LiF (1 nm)/Al (100 nm), wherein the TADF material is the TDS-007 material provided in Synthesis example 1, wherein the luminescent material TDS-007 material accounts for 30% of the total mass and the luminescent material FD-9 accounts for 1% of the total mass.
The following performance measurements were performed on the OLEDs prepared in the above-described verification examples and verification comparative examples:
the driving voltage and current efficiency of the OLED devices prepared in verification examples 1 to 9 and verification comparative examples 1 to 4 were measured using a digital source meter and a luminance meter at the same luminance. Specifically, the voltage is raised at a rate of 0.1V per second, the driving voltage, which is the voltage when the luminance of the OLED device reaches the required luminance, is measured, and the current density at that time is measured; the ratio of brightness to current density is the current efficiency;
OLED performance results
Requiring brightness (cd/m 2) Working voltage (V) Current efficiency (cd/A) External quantum efficiency (%)
Verification example 1 1000 5.2 26.5 20.8
Verification example 2 1000 4.4 27.1 22.6
Verification example 3 1000 4.8 24.8 22.9
Verification example 4 1000 4.9 26.1 23.2
Verification example 5 1000 4.5 25.9 19.3
Verification example 6 1000 5.1 25.6 20.9
Verification example 7 1000 5.7 24.4 22.5
Verification example 8 1000 5.6 24.2 22.6
Verification example 9 1000 5.8 24.3 22.4
Verification example 10 1000 4.5 26.7 23.1
Verification example 11 1000 5.2 23.8 22.1
Verification example 12 1000 5.1 24.7 21.9
Verification example 13 1000 4.3 26.6 21.8
Verification example 14 1000 5.0 25.9 22.1
Verification example 15 1000 5.3 24.5 21.5
Verification example 16 1000 4.6 26.3 19.9
Verification example 17 1000 4.7 26.5 19.6
Verification example 18 1000 4.2 26.4 21.7
Verification example 19 1000 4.3 27.0 21.6
Verification example 20 1000 4.4 26.2 22.6
Comparative example 1 was verified 1000 5.4 8.0 8.08
Comparative example 2 was verified 1000 4.6 10.0 11.3
Comparative example 3 was verified 1000 4.8 12.3 8.06
From the above table, it is seen that the compounds synthesized according to the present invention can sensitize dye effectively when applied to luminescent layer sensitizer in device, and can realize effective energy transfer, thereby obtaining excellent device performance, by comparing verification examples 1 to 20 and verification comparative examples 1 to 3. The result shows that the novel organic material provided by the invention is used for OLED devices, can effectively improve the current efficiency of the devices, and is an OLED material with good performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. A TADF material, characterized in that it is selected from any one of the compounds represented by the following structural formulas:
、/>and->。
2. A superluminescent material for producing a luminescent layer, characterized in that it comprises the TADF material according to claim 1.
3. The super luminescent material for preparing a luminescent layer as claimed in claim 2, further comprising a luminescent material.
4. The super luminescent material for preparing a luminescent layer as claimed in claim 3, comprising 20 to 70 parts by weight of the TADF material, 0.3 to 10 parts by weight of the luminescent material.
5. The super luminescent material for preparing a luminescent layer as claimed in claim 4, comprising 20 to 40 parts by weight of the TADF material, and 0.3 to 5 parts by weight of the luminescent material.
6. The super luminescent material for producing a light-emitting layer according to claim 2, further comprising a host material;
The triplet and singlet energy levels of the host material are higher than the triplet and singlet energy levels of the TADF material, respectively, and the triplet and singlet energy levels of the TADF material are higher than the triplet and singlet energy levels of the light-emitting material, respectively.
7. A transfer material for preparing a transfer layer, characterized in that it comprises the TADF material of claim 1;
the transport layer is an electron transport layer or a hole transport layer.
8. The transport material for preparing a transport layer according to claim 7, wherein the transport material further comprises an electron transport material;
the lowest unoccupied orbitals of the electron transport material are lower than the lowest unoccupied orbitals of the TADF material.
9. The transport material for preparing a transport layer of claim 8, wherein a lowest unoccupied orbital distance difference of the electron transport material from a lowest unoccupied orbital distance of the TADF material is less than 0.5eV.
10. The transport material of claim 7, wherein the transport material further comprises a hole transport material;
the highest occupied track of the hole transport material is higher than the highest occupied track of the TADF material.
11. The transport material of claim 10, wherein the highest occupied rail of the hole transport material differs from the highest occupied rail of the TADF material by less than 0.5eV.
12. An organic electroluminescent device, characterized in that it comprises at least one of the following layered structures:
(1) A light-emitting layer formed of the super luminescent material for preparing a light-emitting layer as claimed in claim 2;
(2) A transfer layer formed of the transfer material for preparing a transfer layer according to claim 7.
13. The organic electroluminescent device of claim 12, wherein the organic electroluminescent device is selected from an organic light emitting diode.
14. The organic electroluminescent device according to claim 12, further comprising a cathode and an anode, wherein at least one layer of the layered structure of (1) or (2) is disposed between the cathode and the anode.
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Publication number Priority date Publication date Assignee Title
CN104725298A (en) * 2015-01-23 2015-06-24 南京工业大学 Carbazole compounds, and synthesis and application thereof in OLEDs (Organic Light-Emitting diodes)
CN108264478A (en) * 2016-12-30 2018-07-10 昆山国显光电有限公司 Carrier transmission material and carrier blocking layers and organic luminescent device
CN109705019A (en) * 2019-01-29 2019-05-03 吉林大学 Benzonitrile derivative and its preparing the application in electroluminescent device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104725298A (en) * 2015-01-23 2015-06-24 南京工业大学 Carbazole compounds, and synthesis and application thereof in OLEDs (Organic Light-Emitting diodes)
CN108264478A (en) * 2016-12-30 2018-07-10 昆山国显光电有限公司 Carrier transmission material and carrier blocking layers and organic luminescent device
CN109705019A (en) * 2019-01-29 2019-05-03 吉林大学 Benzonitrile derivative and its preparing the application in electroluminescent device

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