CN111454263B - Thermally activated delayed fluorescence material, organic light emitting device, and display/illumination device - Google Patents

Thermally activated delayed fluorescence material, organic light emitting device, and display/illumination device Download PDF

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CN111454263B
CN111454263B CN202010375931.5A CN202010375931A CN111454263B CN 111454263 B CN111454263 B CN 111454263B CN 202010375931 A CN202010375931 A CN 202010375931A CN 111454263 B CN111454263 B CN 111454263B
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CN111454263A (en
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蒋佐权
廖良生
屈扬坤
王彤彤
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Suzhou University
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Abstract

The present invention relates to a thermally activated delayed fluorescence material, an organic light emitting device, and a display/illumination device, the thermally activated delayed fluorescence material comprising a compound represented by the following chemical formula (1):
Figure DDA0002476776560000011
wherein G is selected from a direct bond, or a substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene; a is a group with electron-deficient characteristics, and is selected from any one or more of nitrile group, sulfonyl group, carbonyl group, ester group, nitrile aromatic ring, sulfonyl aromatic ring, carbonyl aromatic ring, ester aromatic ring, heteroaryl group or aromatic boron group. The main functional elements of the thermal activation delay fluorescent material are close in space, can realize space non-conjugated charge transfer, have high thermal stability, high glass transition temperature and excellent luminescence performance, and can be effectively applied to organic light-emitting devices.

Description

Thermally activated delayed fluorescence material, organic light emitting device, and display/illumination device
Technical Field
The invention relates to the field of electroluminescent materials, in particular to a thermally activated delayed fluorescence material, an organic light-emitting device and a display/illumination device.
Background
The organic semiconductor material has rich diversity and derivatization, can flexibly regulate and control the molecular structure according to application requirements, has lower preparation cost and excellent photoelectric property, and can be widely applied to organic light-emitting diodes (Organic Light Emitting Diode, OLED for short). Organic light-emitting materials and OLED devices have great application potential and have attracted extensive attention and research by students at home and abroad over the past 30 years.
Organic luminescent materials that are commercially available today are based on conventional fluorescent and phosphorescent materials. Wherein, traditional fluorescent material is comparatively stable, the cost is lower. According to spin law, the ratio of singlet excitons to triplet excitons generated by combining electrons and holes is 1:3, whereas conventional fluorescent materials can only utilize 25% of the electrically induced singlet excitons, and 75% of the triplet excitons are consumed in a non-radiative transition form, so that the efficiency is lower. The phosphorescent material successfully utilizes singlet excitons and triplet excitons by introducing noble metals such as iridium, platinum and the like, and can theoretically reach 100% internal quantum efficiency. Noble metals are rare and expensive, metal complexes are complex to synthesize and are not stable enough, limiting the large-scale application of phosphorescent OLEDs.
In order to develop more efficient and stable organic luminescent materials, the japanese teaching Adachi found thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) materials based on triplet-singlet transitions. In TADF materials, a very small triplet-singlet energy level difference (Δe) is achieved by separating the electron donating element (D) and the electron withdrawing element (a) ST ). The current method is to connect D/A through conjugated bridge (pi) to transfer electron from D to A through conjugation, forming charge transfer state luminescence.
However, the TADF materials constructed based on the D-pi-A method still have a plurality of problems at present, and D/A separation leads to the reduction of resonance factors, so that materials with higher efficiency are still relatively scarce. Devices based on the materials have shorter service lives and larger roll-off. Thus, there is still a need for improvements and developments in the art, particularly in the construction of materials.
Disclosure of Invention
The invention aims to provide a thermal activation delay fluorescent material, an organic light-emitting device and a display/lighting device, wherein the thermal activation delay fluorescent material realizes intramolecular charge interaction through space unconjugated connection, unlike a classical D-pi-A structure. The structural compound has excellent luminescence property and can be effectively applied to an organic light-emitting device.
In order to achieve the above purpose, the present invention provides the following technical solutions: a thermally activated delayed fluorescence material comprising a compound represented by the following chemical formula (1) and a stereoisomer:
Figure BDA0002476776540000021
chemical formula (1)
G is selected from a direct bond, or a substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene;
a is a group with electron-deficient characteristics, which is selected from any one or more of nitrile group, sulfonyl group, carbonyl group, ester group, nitrile aromatic ring, sulfonyl aromatic ring, carbonyl aromatic ring, ester aromatic ring, heteroaryl group or aromatic boron group;
R’，R”，R 1 to R 18 Are identical to or different from each other and are each independently hydrogen, deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amine group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; a substituted or unsubstituted alkylsulfonyl group; a substituted or unsubstituted arylsulfonyl group; a substituted or unsubstituted alkenyl group; substituted or unsubstituted aralkyl; substituted or unsubstituted aralkenyl; substituted or unsubstituted alkyl An aryl group; a substituted or unsubstituted alkylamino group; substituted or unsubstituted aralkylamino; substituted or unsubstituted heteroarylamino; substituted or unsubstituted arylamino; substituted or unsubstituted arylheteroarylamino; substituted or unsubstituted aryl phosphino; a substituted or unsubstituted phosphine oxide group; substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or optionally with an adjacent group to form a ring.
The invention also provides an organic light-emitting device, which comprises a first electrode and a second electrode which are oppositely arranged, wherein an organic material layer is arranged between the first electrode and the second electrode, the organic material layer comprises a light-emitting layer, and the light-emitting layer comprises the thermal activation delay fluorescent material.
Further, the light emitting layer is composed of a sensitized material, a light emitting material, and a host material, and the thermally activated delayed fluorescence material is used as any one or more of the host materials, and/or the light emitting material.
Further, the organic material layer further comprises a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer and an electron injection layer, and the organic light emitting device is sequentially provided with the second electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer and the first electrode from the height direction.
Further, the thermally activated delayed fluorescence material is contained in any one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
The invention also provides a display/lighting device comprising the organic light emitting device.
Compared with the prior art, the invention has the beneficial effects that: the thermal activation delay fluorescent material realizes a space charge transfer mechanism in molecules through space non-conjugated connection. The invention introduces D in the spiro structure, introduces A in the 1 position of fluorene, and spatially separates D/A directly to ensure smaller delta E ST . At the same time, two planes in the screw ring are utilized to be verticalThe spatial rotation of D and A in the molecule is limited, so that the distance between planes of the D/A is reduced, the spatial interaction is realized, and the fluorescence quantum yield of the material is improved. The material has excellent luminescence property, and can be used as a material of an organic material layer in an organic light-emitting device, in particular a luminescent material and a main material in a luminescent layer. The compound according to at least one exemplary embodiment of the present specification may realize high efficiency of thermally activated delayed fluorescence and achieve high efficiency of an organic light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification may realize a high-efficiency fluorescent light-emitting device.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 shows one example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a light-emitting layer 3, and a negative electrode 4;
fig. 2 shows an example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a negative electrode 4.
Reference numerals
1: substrate
2: positive electrode
3: hole injection layer
4: hole transport layer
5: light-emitting layer
6: electron transport layer
7: negative electrode
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Term interpretation of the present specification:
"substituted or unsubstituted" in the present invention means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amine group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; aralkylamino groups; a heteroarylamino group; an arylamino group; aryl phosphino; and a heterocyclic group, or a substituent which is unsubstituted or linked via two or more substituents among the above-exemplified substituents. For example, a "substituent to which two or more substituents are attached" may be an aryl group substituted with a heteroaryl group. That is, biphenyl may also be aryl, and may be interpreted as two substituents to which phenyl is attached.
"halogen radicals" in the context of the present invention comprise fluorine, chlorine, bromine or iodine.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structure, but is not limited thereto.
Figure BDA0002476776540000041
In the present specification, for the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto.
Figure BDA0002476776540000042
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structure, but is not limited thereto.
Figure BDA0002476776540000043
In the present specification, the number of carbon atoms of the amide group is not particularly limited, but is preferably 1 to 25. Specifically, the amide group may be a compound having the following structure, but is not limited thereto.
Figure BDA0002476776540000051
In the present specification, the silyl group may be represented by the formula-SiR a R b R c R represents a 、R b And R is c Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
In the present specification, the boron group may be represented by the formula-BR a R b R represents a 、R b Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the boron group include, but are not limited to, dimethylboronyl, diethylboronyl, t-butylmethylboronyl, diphenylboronyl, phenylboronyl, and the like.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to one exemplary embodiment, the alkyl group has a carbon number of 1 to 20. According to another exemplary embodiment, the alkyl group has a carbon number of 1 to 10. According to yet another exemplary embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
Substituents described in this specification that contain alkyl, alkoxy and other alkyl moieties include both straight chain and branched forms.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to one exemplary embodiment, the alkenyl group has a carbon number of 2 to 20. According to another exemplary embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another exemplary embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 40. According to another exemplary embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 20. According to yet another exemplary embodiment, the cycloalkyl group has a number of carbon atoms of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present specification, the number of carbon atoms of the alkylamino group is not particularly limited, but is preferably 1 to 40. Specific examples of the alkylamino group include, but are not limited to, methylamino group, dimethylamino group, ethylamino group, diethylamino group, phenylamino group, naphthylamino group, biphenylamino group, anthracenylamino group, 9-methyl-anthracenylamino group, diphenylamino group, phenylnaphthylamino group, xylylamino group, phenyltolylamino group, triphenylamino group, and the like.
In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. An arylamine group containing two or more aryl groups can contain a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
Specific examples of the arylamino group include, but are not limited to, a phenylamino group, a naphthylamino group, a biphenylamino group, an anthrylamino group, a 3-methyl-phenylamino group, a 4-methyl-naphthylamino group, a 2-methyl-biphenylamino group, a 9-methyl-anthrylamino group, a diphenylamino group, a phenylnaphthylamino group, a xylylamino group, a phenyltolylamino group, a carbazolyl group, a triphenylamino group, and the like.
In the present specification, examples of the heteroarylamino group include a substituted or unsubstituted mono-heteroarylamino group, a substituted or unsubstituted di-heteroarylamino group, or a substituted or unsubstituted tri-heteroarylamino group. Heteroaryl groups in the heteroarylamine group may be monocyclic heterocyclic groups or polycyclic heterocyclic groups. The heteroarylamine group comprising two or more heterocyclic groups may comprise a monocyclic heterocyclic group, a polycyclic heterocyclic group, or both a monocyclic heterocyclic group and a polycyclic heterocyclic group.
In the present specification, examples of the arylphosphino group include a substituted or unsubstituted monoarylphosphino group, a substituted or unsubstituted diarylphosphino group, or a substituted or unsubstituted triarylphosphino group. The aryl group in the aryl phosphino group may be a monocyclic aryl group or a polycyclic aryl group. An arylphosphino group comprising two or more aryl groups may comprise a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one exemplary embodiment, the aryl group has a carbon number of 6 to 30. According to one exemplary embodiment, the aryl group has 6 to 20 carbon atoms. When the aryl group is a monocyclic aryl group, examples of the monocyclic aryl group include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Examples of polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, indenyl,
Figure BDA0002476776540000071
Radicals, fluorenyl radicals, triphenylene radicals, and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.
When the fluorenyl group is substituted, the fluorenyl group may be
Figure BDA0002476776540000072
Figure BDA0002476776540000073
And +.>
Figure BDA0002476776540000074
However, the fluorenyl group is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing one or more of N, O, P, S, si and Se as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. According to one exemplary embodiment, the heterocyclyl has a number of carbon atoms from 1 to 30. Examples of heterocyclyl groups include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, noisyl, indolizinyl, oxazinyl, phthalazinyl, acridinopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, indolocarbazolyl, imidazoyl, phenanthridinyl, and the like.
In this specification, the above description of heterocyclyl groups may be applied to heteroaryl groups, except that heteroaryl groups are aromatic.
In the present specification, the above description of aryl groups can be applied to aryl groups in aryloxy groups, arylthio groups, arylsulfonyl groups, arylphosphino groups, aralkyl groups, aralkylamino groups, aralkenyl groups, alkylaryl groups, arylamino groups, and arylheteroarylamino groups.
In the present specification, the above description of the alkyl group may be applied to the alkyl group in the alkylthio group, the alkylsulfonyl group, the aralkyl group, the aralkylamino group, the alkylaryl group, and the alkylamino group.
In this specification, the above description of heterocyclyl groups may be applied to heteroaryl groups in heteroaryl, heteroarylamine and arylheteroarylamine groups.
In the present specification, germanium groups may be represented byStudy type-GeR a R b R c R represents a 、R b And R is c Each may be hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the germanium group include trimethylgermanium group, triethylgermanium group, t-butyldimethylgermanium group, and the like, but are not limited thereto.
In the present specification, the above description of alkenyl groups may be applied to alkenyl groups in aralkenyl groups.
In the present specification, the above description of aryl groups can be applied to arylene groups, except that arylene groups are divalent.
In this specification, the above description of heteroaryl groups may be applied to heteroarylene groups, except that the heteroarylene group is divalent.
In the present specification, the meaning of bonding with an adjacent group to form a ring means bonding with an adjacent group to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; a substituted or unsubstituted aromatic heterocycle; or a fused ring thereof.
In the present specification, an aliphatic hydrocarbon ring means a ring of a non-aromatic group constituted of only carbon atoms and hydrogen atoms as a ring. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1, 4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like, but are not limited thereto.
In the present specification, an aromatic hydrocarbon ring means an aromatic ring composed of only carbon atoms and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, benzophenanthrene, phenalene, pyrene, tetracene,
Figure BDA0002476776540000081
Pentacene, fluorene, indene, acenaphthylene, benzofluorene, spirofluorene, etc., but is not limited thereto.
In the present specification, an aliphatic heterocyclic ring means an aliphatic ring containing one or more hetero atoms. Specifically, examples of the aliphatic heterocycle include ethylene oxide, tetrahydrofuran, 1, 4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azacyclooctane, thiacyclooctane, and the like, but are not limited thereto.
In this specification, an aromatic heterocycle means an aromatic ring containing one or more heteroatoms. Specifically, examples of the aromatic heterocycle include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, pyrimidine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, acridine, phenanthridine, naphthyridine, triazaindene, indole, indolizine, benzothiazole, benzoxazole, benzimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole, benzocarbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, phenanthridine, indenocarbazole, and the like, but are not limited thereto.
In the present specification, aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic heterocyclic ring and aromatic heterocyclic ring may be monocyclic or polycyclic.
In the structural formula, any one carbon is a linking moiety for forming a monovalent group, and the remaining carbons are hydrogen or a group to which one or two or more of substituents (e.g., halogen group, nitrile group, alkyl group, silyl group, arylamino group, arylphosphine group, aryl group, and heteroaryl group) are bonded.
According to an exemplary embodiment of the present invention, in the chemical formula (1), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group.
According to an exemplary embodiment of the present invention, in the chemical formula (1), G may be selected from a direct bond or the following structural formula.
Figure BDA0002476776540000091
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Figure BDA0002476776540000101
According to an exemplary embodiment of the present invention, in the general formula (1), a is selected from the following structural formulas.
Figure BDA0002476776540000102
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Figure BDA0002476776540000111
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Figure BDA0002476776540000121
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Figure BDA0002476776540000131
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Figure BDA0002476776540000141
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Figure BDA0002476776540000151
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Figure BDA0002476776540000161
Preferably, the thermally activated delayed fluorescence material is preferably the following compound:
Figure BDA0002476776540000171
Figure BDA0002476776540000181
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Figure BDA0002476776540000191
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Figure BDA0002476776540000201
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Figure BDA0002476776540000211
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Figure BDA0002476776540000221
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Figure BDA0002476776540000231
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Figure BDA0002476776540000241
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Figure BDA0002476776540000251
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Figure BDA0002476776540000261
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Figure BDA0002476776540000271
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Figure BDA0002476776540000281
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Figure BDA0002476776540000291
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Figure BDA0002476776540000301
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Figure BDA0002476776540000311
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Figure BDA0002476776540000321
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Figure BDA0002476776540000331
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Figure BDA0002476776540000341
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Figure BDA0002476776540000351
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Figure BDA0002476776540000361
wherein the compounds represented by the above structural formula may be substituted on each carbon atom thereof, preferably hydrogen, cyano, substituted or unsubstituted C1-C10 aliphatic group, C6-C24 arylamine group, C6-C24 aryl group, C4-C24 heteroaryl group, pyridine, thiophene and the like.
The compound of formula (1) may be prepared by the following reaction scheme.
[ reaction chemical formula ]
Figure BDA0002476776540000362
In the reaction, R 1 To R 18 The same as those defined in the chemical formula (1). The reaction formula relates to an example in which a specific substituent is introduced, but a person skilled in the art may introduce a substituent without using a technique known in the art, if necessary, and in introducing a substituent, the introduction may be performed by changing the kind or number of substituents. Furthermore, the introduction may be performed by a person skilled in the art by varying the sample, reaction conditions or starting materials of the following reaction formula using techniques known in the art.
For example, the compound represented by the formula (1) may be prepared according to the above reaction formula, substituents may be bonded thereto using methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art. The substituent may be bonded according to the above reaction chemical formula, however, the reaction is not limited thereto.
Figure BDA0002476776540000371
Chemical formula (1)
The invention also provides an organic electroluminescent device prepared based on the thermally activated delayed fluorescence material, which comprises a second electrode and a first electrode which are oppositely arranged, wherein one or more organic material layers are arranged between the second electrode and the first electrode, the organic material layers comprise a light-emitting layer, and the light-emitting layer comprises the thermally activated delayed fluorescence material. Wherein the luminescent layer is composed of a sensitized material, a luminescent material and a host material, and the thermally activated delayed fluorescence material is any one or more of the luminescent material and/or the host material. The organic material layer further comprises a hole injection layer, a hole transmission layer, an electron blocking layer, an electron transmission layer and an electron injection layer, and the organic light-emitting device is sequentially provided with the second electrode, the hole injection layer, the hole transmission layer, the electron blocking layer, the light-emitting layer, the electron transmission layer, the electron injection layer and the first electrode from the height direction. Of course, the thermally activated delayed fluorescence material may be provided in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer, in addition to the thermally activated delayed fluorescence material described above. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers.
In this specification, when one member is provided "on" another member, this includes not only a case where one member is in contact with another member but also a case where another member exists between two members.
In this specification, when a portion "comprises" one constituent element, unless specifically described otherwise, this is not intended to exclude another constituent element, but is intended to also include another constituent element.
In one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer composed of a host material and a guest light emitting material (doping ratio range, optimally 10% -70%) including the compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer composed of a host material and a guest light emitting material, and the host material includes a compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer is composed of a single component of a light emitting material including the compound of formula (1).
In the present specification, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor, and an organic transistor.
Hereinafter, an organic light emitting device will be described.
An exemplary embodiment of the present specification provides an organic light emitting device including a first electrode; a second electrode disposed to face; a light emitting layer disposed between the first electrode and the second electrode; and two or more organic material layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers contains a heterocyclic compound. In one exemplary embodiment, the two or more organic material layers may be selected from: an electron transport layer, an electron injection layer, a layer that simultaneously transports and injects electrons, a hole injection layer, a hole transport layer, and a hole blocking layer.
In one exemplary embodiment of the present specification, the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes a heterocyclic compound. Specifically, in one exemplary embodiment of the present specification, the heterocyclic compound may be further included in one of two or more electron transport layers, and may be included in each of the two or more electron transport layers.
Further, in one exemplary embodiment of the present specification, when a heterocyclic compound is included in each of two or more electron transport layers, other materials than the heterocyclic compound may be the same as or different from each other.
In another exemplary embodiment, the organic light emitting device may be an organic light emitting device (normal type) having a structure in which a positive electrode, one or more organic material layers, and a negative electrode are sequentially stacked on a substrate.
In still another exemplary embodiment, the organic light emitting device may be an organic light emitting device (inverted type) having a reverse structure in which a negative electrode, one or more organic material layers, and a positive electrode are sequentially stacked on a substrate.
For example, a structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in fig. 1 and 2.
Fig. 1 shows an exemplary embodiment of an organic light emitting device constituted by a substrate 1, a positive electrode 2, a light emitting layer 3, and a negative electrode 4. In the structure as described above, the compound may be contained in the light emitting layer.
Fig. 2 shows an exemplary embodiment of an organic light emitting device constituted by a substrate 1, a positive electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a negative electrode 7. In the structure described above, the compound may be contained in one or more of a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.
The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers include the compound of the present specification, i.e., the compound of formula (1).
When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device may be manufactured by the following method: the positive electrode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the positive electrode, and then depositing a material usable as a negative electrode on the organic material layer. In addition to the method described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.
In addition, in manufacturing an organic light emitting device, the compound of formula (1) may be formed into an organic material layer not only by a vacuum deposition method but also by a solution method. Here, the solution method means spin coating, dip coating, knife coating, ink jet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
In addition to the method described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate (international publication No. 2003/012890). However, the manufacturing method is not limited thereto.
In one exemplary embodiment of the present description, the first electrode is a positive electrode and the second electrode is a negative electrode.
In another exemplary embodiment of the present specification, the first electrode is a negative electrode and the second electrode is a positive electrode.
As the positive electrode material, a material having a large work function is generally preferable to smoothly inject holes into the organic material layer. Specific examples of positive electrode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO, al or SnO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, polyaniline, and the like, but is not limited thereto.
As the negative electrode material, a material having a small work function is generally preferable to smoothly inject electrons into the organic material layer. Specific examples of the negative electrode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al, etc., but is not limited thereto.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has an effect of injecting holes in the positive electrode, and has an excellent hole injection effect to the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and also has an excellent thin film forming capability. It is preferred that the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transporting layer is a layer that receives holes from the hole injecting layer and transports the holes to the light emitting layer, and the hole transporting material is such a suitable material: which can receive holes from the positive electrode or the hole injection layer, transfer holes to the light emitting layer, and have a high mobility to holes. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which both a common moiety and a non-common moiety exist, and the like, but are not limited thereto.
The light emitting layer may comprise a host material and a dopant material, and the dopant material may comprise a doped light emitting material and a doped sensitizer material. The host material is preferably an organic compound material, and a host material containing a metal complex may be used. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant that primarily satisfies the triplet criteria.
Examples of the organic compound host material include fused aromatic ring derivatives, heterocyclic ring-containing compounds, or the like. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.
Examples of organic compounds used as hosts are selected from: a group consisting of the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,
Figure BDA0002476776540000401
Perylene and azulene; a group consisting of the following aromatic heterocyclic compounds: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyridobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinolineIsoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonephthalenyl, phosphino, and combinations thereof.
According to one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by chemical formula (1) as a doped light emitting material.
According to another exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by chemical formula (1) as a host material.
The light emitting layer may include a host material and a dopant material. The dopant emitting material is preferably such that: which can receive holes and electrons respectively transported by the hole transport layer and the electron transport layer and combine the holes with electrons to emit light in the visible light region, and has good quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; a dimeric styryl compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzoxazole, benzothiazole and benzimidazole based compounds; poly (p-phenylene vinylene) (PPV) based polymers; a spiro compound; polyfluorene, rubrene, etc., but notAnd is not limited thereto.
The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by chemical formula (1).
When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is such a suitable material: which can well inject electrons from the negative electrode and can transfer electrons to the light emitting layer, and has a high mobility for electrons. Specific examples thereof include: al complex of 8-hydroxyquinoline containing Alq 3 But not limited to, complexes of (c) and (d), organic radical compounds, hydroxyflavone-metal complexes, and the like. The electron transport layer may be used with any desired first electrode material as used according to the related art. In particular, suitable examples of the first electrode material are typical materials having a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from the negative electrode, and has an excellent electron injection effect to the light emitting layer or light emitting material, prevents excitons generated in the light emitting layer from moving to the hole injection layer, and also has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like, but are not limited thereto.
The organic light emitting device according to the present specification may be of a top emission type, a bottom emission type, or a dual emission type, depending on the materials used.
In this specification, the compound of formula (1) may be contained in an organic solar cell or an organic transistor in addition to an organic light emitting device.
The preparation of the compound represented by chemical formula (1) and the organic light emitting device including the same will be specifically described in the following examples. However, the following examples are provided for illustrating the present specification, and the scope of the present specification is not limited thereby.
Preparation example
Synthesis example
The reaction formula relates to an example in which a specific substituent is introduced, but a person skilled in the art may introduce a substituent without using a technique known in the art, if necessary, and in introducing a substituent, the introduction may be performed by changing the kind or number of substituents. Furthermore, the introduction may be performed by a person skilled in the art by varying the sample, reaction conditions or starting materials of the following reaction formula using techniques known in the art.
< preparation example 1> Synthesis of Compound 1 below
Figure BDA0002476776540000421
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.98 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 1 (7.89 g,19.20mmol, yield about 86%) which was dried for use. 3, 6-Di-tert-butylcarbazole (7.00 g,25.05 mmol), 1-bromo-2-fluorobenzene (8.77 g,50.10 mmol), cesium carbonate (24.16 g,125.26 mmol) were placed in a 500mL round bottom flask under nitrogen and 350mL dimethylformamide was added. The above mixture was heated to reflux for 12 hours. After the reaction, the temperature is reduced to room temperature, the mixture is filtered and washed by a large amount of distilled water, and then The reaction mixture was then recrystallized from methylene chloride/ethanol to give intermediate 2 (9.21 g,16.97mmol, yield about 85%) which was dried for further use. Intermediate 2 (7.92 g,18.23 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (7.60 mL,18.23 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 1 (5.00 g,12.15 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 1 (7.58 g,10.12mmol, yield: about 83%). MS [ M+H ]] + ＝748。
< preparation example 2> Synthesis of Compound 2 below
Figure BDA0002476776540000431
3, 6-diphenylcarbazole (7.00 g,21.92 mmol), 1-bromo-2-fluorobenzene (7.67 g,43.83 mmol), cesium carbonate (21.14 g,109.58 mmol) were placed in a 500mL round bottom flask under nitrogen and 350mL dimethylformamide was added. The above mixture was heated to reflux for 12 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 3 (9.60 g,20.24mmol, yield about 92%) which was dried for use. Intermediate 3 (8.65 g,18.23 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (7.60 mL,18.23 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 1 (5.00 g,12.15 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was decompressed and removed After tetrahydrofuran was removed, 40mL of dichloromethane was added to extract 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 degrees celsius for reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 2 (8.02 g,10.17mmol, yield about 84%). MS [ M+H ]] + ＝788。
< preparation example 3> Synthesis of Compound 3 below
Figure BDA0002476776540000441
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 2- (4-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.66 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 4 (8.70 g, yield about 80%) which was dried for use. 3, 6-Dimethylcarbazole (5.00 g,25.61 mmol), 1-bromo-2-fluorobenzene (8.96 g,51.21 mmol), cesium carbonate (24.70 g,128.03 mmol) were placed in a 500mL round bottom flask under nitrogen and 350mL dimethylformamide was added. The above mixture was heated to reflux for 12 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 5 (7.33 g,20.93mmol, yield about 82%) which was dried for use. Under the protection of nitrogen, placing the intermediate 5 (5.39 g,15.38 mmol) into a 250mL two-port bottle, adding 77mL anhydrous tetrahydrofuran for dissolution, then placing at minus 78 ℃, dropwise adding 2.4M n-butyllithium solution (6.41 mL,15.38 mmol) at the concentration of minus 78 ℃, stirring at minus 78 ℃ for 1 hour, adding the intermediate 4 (5.00 g,10.26 mmol), stirring overnight, adding 20mL distilled water for quenching . The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 3 (6.12 g,8.26mmol, yield about 81%). MS [ M+H ]] + ＝741。
< preparation example 4> Synthesis of Compound 4 below
Figure BDA0002476776540000451
Intermediate 2 (6.68 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 4 (5.00 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to give compound 4 (7.05 g,8.54mmol, yield: about 83%). MS [ M+H ] ] + ＝825。
< preparation example 5> Synthesis of Compound 5 below
Figure BDA0002476776540000452
Intermediate 3 (7.30 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen blanketAfter 77mL of anhydrous tetrahydrofuran was added thereto for dissolution, the mixture was left at minus 78℃and then a 2.4M n-butyllithium solution (6.41 mL,15.38 mmol) was added dropwise thereto, followed by stirring at minus 78℃for 1 hour, then intermediate 4 (5.00 g,10.26 mmol) was added thereto, and after stirring overnight, 20mL of distilled water was added thereto for quenching. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain Compound 5 (7.12 g,8.23mmol, yield about 80%). MS [ M+H ]] + ＝865。
< preparation example 6> Synthesis of the following Compound 6
Figure BDA0002476776540000461
9'H-9,3':6', 9' -tricarbazole (7.00 g,14.07 mmol), 1-bromo-2-fluorobenzene (4.92 g,28.13 mmol), cesium carbonate (13.57 g,70.34 mmol) were placed in a 500mL round bottom flask under nitrogen and 350mL dimethylformamide was added. The above mixture was heated to reflux for 12 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 6 (7.89 g,12.09mmol, yield about 86%) which was dried for use. Intermediate 6 (10.04 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 4 (5.00 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane, extracting for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, filtering, drying to obtain solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, and stirring After 10 minutes 3mL of concentrated hydrochloric acid was added and heated to 110 degrees celsius for 3 hours at reflux. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain Compound 6 (9.34 g,8.95mmol, yield: about 87%). MS [ M+H ]] + ＝1043。
< preparation example 7> Synthesis of the following Compound 7
Figure BDA0002476776540000471
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 2- (3-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.66 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 7 (8.27 g, yield about 76%) which was dried for use. Intermediate 2 (6.68 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 7 (5.00 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 7 (7.40 g,8.97mmol, yield about 87%). MS [ M+H ] ] + ＝825。
< preparation example 8> Synthesis of Compound 8 below
Figure BDA0002476776540000481
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 2- (4-chlorophenyl) -4, 6-diphenyl-1, 5-pyrimidine (8.63 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 8 (8.68 g, yield about 80%) which was dried for use. Intermediate 2 (6.68 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 8 (4.97 g,10.26 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 8 (7.03 g,8.52mmol, yield: about 83%). MS [ M+H ] ] + ＝823。
< preparation example 9> Synthesis of the following Compound 9
Figure BDA0002476776540000491
Under the protection of nitrogen, placing the intermediate 3 (7.30 g,15.38 mmol) into a 250mL two-port bottle, adding 77mL anhydrous tetrahydrofuran for dissolution, then placing at minus 78 ℃ and dropwise adding n-butyl with the concentration of 2.4MLithium solution (6.41 mL,15.38 mmol), after stirring at-78℃for 1 hour, intermediate 4 (4.97 g,10.26 mmol) was added, and after stirring overnight, 20mL of distilled water was added for quenching. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 9 (7.47 g,8.64mmol, yield about 84%). MS [ M+H ]] + ＝863。
< preparation example 10> Synthesis of the following Compound 10
Figure BDA0002476776540000492
Intermediate 6 (10.04 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 4 (4.97 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 10 (8.41 g,8.01mmol, yield about 78%). MS [ M+H ] ] + ＝1041。
< preparation example 11> Synthesis of Compound 11 below
Figure BDA0002476776540000501
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 1-bromo-4- (phenylsulfonyl) benzene (6.63 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen, and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 9 (6.63 g,16.74mmol, yield about 75%) which was dried for use. Intermediate 2 (6.68 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 9 (4.07 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 11 (6.12 g,8.34mmol, yield: about 81%). MS [ M+H ] ] + ＝734。
< preparation example 12> Synthesis of the following Compound 12
Figure BDA0002476776540000511
Under the protection of nitrogen, placing the intermediate 6 (10.04 g,15.38 mmol) into a 250mL two-port bottle, adding 77mL anhydrous tetrahydrofuran for dissolution, then placing at minus 78 ℃, dropwise adding 2.4M n-butyllithium solution (6.41 mL,15.38 mmol) at minus 78 ℃, stirring at minus 78 ℃ for 1 hour, adding the intermediate 9 (4.07 g,10.26 mmol), stirring overnight, addingQuench with 20mL distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 12 (8.25 g,8.66mmol, yield about 84%). MS [ M+H ]] + ＝952。
< preparation example 13> Synthesis of Compound 13 below
Figure BDA0002476776540000512
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 2- (4-bromophenyl) -xanthone (11.76 g,33.48 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.17 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 10 (9.14 g,20.29mmol, yield about 91%) which was dried for use. Intermediate 6 (10.04 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, intermediate 10 (4.62 g,10.26 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature is reduced to room temperature, the reaction solution is poured into 500mL of ice water, the product is separated out, and dichloro is used after suction filtration Silica gel column chromatography of the eluent in the mixture ratio of methane and petroleum ether gave compound 13 (9.10 g,9.04mmol, yield about 88%). MS [ M+H ]] + ＝1006。
< preparation example 14> Synthesis of the following Compound 14
Figure BDA0002476776540000521
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 4-bromoxynil (6.06 g,33.48 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.17 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization and purification with methylene chloride/ethanol to give intermediate 11 (5.65 g,20.1mmol, yield about 90%) which was dried for use. Intermediate 6 (10.04 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 11 (2.88 g,10.26 mmol) was added, and after stirring overnight, 20mL of distilled water was added to quench the mixture. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 14 (7.70 g,9.20mmol, yield about 89%). MS [ M+H ] ] + ＝836。
< preparation example 15> Synthesis of the following Compound 15
Figure BDA0002476776540000531
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), (4-bromophenyl) dimethylboron (9.04 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization and purification with methylene chloride/ethanol to give intermediate 12 (10.12 g,20.06mmol, yield about 90%), which was dried for use. Intermediate 2 (6.68 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 12 (5.17 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 15 (6.81 g,8.10mmol, yield: about 79%). MS [ M+H ] ] + ＝841。
< preparation example 16> Synthesis of the following Compound 16
Figure BDA0002476776540000541
Intermediate 6 (10.04 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 12 (5.17 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was decompressed to remove tetrahydrofuranAfter extraction of the pyran with 40mL of methylene chloride 3 times, methylene chloride was removed under reduced pressure, ethanol was added for recrystallization, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added and stirred for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110℃for reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 16 (8.91 g,8.41mmol, yield about 82%). MS [ M+H ]] + ＝1059。
< preparation example 17> Synthesis of the following Compound 17
Figure BDA0002476776540000542
9-fluorenone-1-boronic acid (5.0 g,22.32 mmol), 3, 5-dicyanochlorobenzene (3.63 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen, and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, suction filtration and washing with a large amount of distilled water, followed by recrystallization from methylene chloride/ethanol to obtain intermediate 13 (5.80 g,18.93mmol, yield about 85%) which was dried for use. Intermediate 3 (7.30 g,15.38 mmol) was placed in a 250mL two-port flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 13 (3.14 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction solution is poured into 500mL of ice water, the product is separated out, and after suction filtration, the silica gel column chromatography is carried out by using a eluent with the mixture ratio of dichloromethane and petroleum ether to obtain the compound 17 (5.96 g,8.72mmol, yield about 85%). MS [ M+H ]] + ＝683。
< preparation example 18> Synthesis of the following Compound 18
Figure BDA0002476776540000551
Intermediate 6 (10.01 g,15.38 mmol) was placed in a 250mL two-necked flask under nitrogen, 77mL of anhydrous tetrahydrofuran was added to dissolve the intermediate, then a 2.4M solution of n-butyllithium (6.41 mL,15.38 mmol) was added dropwise at-78deg.C, stirred for 1 hour at-78deg.C, then intermediate 13 (3.14 g,10.26 mmol) was added, stirred overnight, and then quenched with 20mL of distilled water. The reaction solution was subjected to reduced pressure to remove tetrahydrofuran, 40mL of dichloromethane was added to extract for 3 times, dichloromethane was removed under reduced pressure, ethanol was added to recrystallize, and the solid obtained after suction filtration and drying was placed in a 250mL flask, 100mL of acetic acid was added to stir for 10 minutes, 3mL of concentrated hydrochloric acid was added and heated to 110 ℃ to reflux for 3 hours. After the reaction, the temperature was lowered to room temperature, the reaction solution was poured into 500mL of ice water, the product was precipitated, and after suction filtration, silica gel column chromatography was performed with a eluent of dichloromethane and petroleum ether ratio to obtain compound 18 (7.07 g,8.21mmol, yield about 80%). MS [ M+H ]] + ＝861。
Figure BDA0002476776540000561
Comparative example of one exemplary example preparation method:
by way of comparison, the following route was followed with the molecule of example 1
Comparative example 1 Synthesis of Compound 1 below
Figure BDA0002476776540000571
(3 ',6' -Di-tert-butylspiro [ fluorene-9, 8' -indol [3,2,1] acridin ] -1-yl) boronic acid (12.53 g,22.32 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.98 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, no new product was obtained by thin plate chromatography, and the yield was 0.
Comparative example 2 Synthesis of Compound 1 below
Figure BDA0002476776540000572
1-bromo- (3 ',6' -di-tert-butylspiro [ fluorene-9, 8' -indole [3,2,1] acridine ]) (13.28 g,22.32 mmol), 4, 6-diphenyl-1, 3, 5-triazine-2-boronic acid (6.18 g,22.32 mmol), tetrakis (triphenylphosphine) palladium (773.39 mg,0.67 mmol), anhydrous potassium carbonate (6.16 g,44.64 mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, no new product was obtained by thin plate chromatography, and the yield was 0.
Examples 1-1 to 1-18
Experimental example 1-1
The compound of the present invention is purified by sublimation in high purity by the existing method, and then an organic light emitting device is manufactured by the following method.
Thin coating with a thickness of
Figure BDA0002476776540000573
The glass substrate of Indium Tin Oxide (ITO) was put into distilled water in which a cleaning agent was dissolved and subjected to ultrasonic washing. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed with isopropanol, acetone, and methanol solvents, and drying was performed. The substrate is then transferred to a plasma cleaner. In addition, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
Heating 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) of the following chemical formulaVacuum on the transparent ITO electrode prepared in this way to a thickness of
Figure BDA0002476776540000581
As a hole injection layer.
Figure BDA0002476776540000582
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BDA0002476776540000583
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BDA0002476776540000584
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was allowed to occur
Figure BDA0002476776540000589
Vacuum deposition is carried out on the hole transport layer to form an electron blocking layer. />
Figure BDA0002476776540000585
Then, compound 1 and bis [2- ((oxo) diphenylphosphino) phenyl]Ether (DPEPO) was vacuum deposited on the exciton blocking layer at a weight ratio of 3:7 to a thickness of
Figure BDA0002476776540000586
Thereby forming a light emitting layer.
Figure BDA0002476776540000587
The following electron-transporting materials 1,3, 5-tris [ (3-pyrazine)Pyridyl) -3-phenyl group]Benzene (TmPyPB)
Figure BDA0002476776540000588
And vacuum depositing on the light-emitting layer to form an electron transport layer.
Figure BDA0002476776540000591
The compound lithium 8-hydroxyquinoline (Liq)
Figure BDA0002476776540000592
And metallic aluminum->
Figure BDA0002476776540000593
Sequentially deposited on the electron transport layer as an electron injection layer and a negative electrode.
Figure BDA0002476776540000594
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material Liq are kept at
Figure BDA0002476776540000595
Second to->
Figure BDA0002476776540000596
Organic functional layer material comprising hole transport layer material, electron blocking layer material, light emitting layer material, electron transport layer material, deposition rate is kept +.>
Figure BDA0002476776540000597
Second to->
Figure BDA0002476776540000598
The deposition rate of the electrode material metallic aluminium is kept +.>
Figure BDA00024767765400005910
Second to->
Figure BDA0002476776540000599
Per second, and maintains the vacuum level during deposition at 1X 10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Experimental examples 1-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 2 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 3 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 4
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 4 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 5 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 6
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 6 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 7
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 7 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 8
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 8 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 9
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 9 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 10 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 11 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 12
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 12 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 13
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 13 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 14
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 14 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 15
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 15 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 16
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 16 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 17
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 17 was used instead of compound 1 in experimental example 1-1.
Experimental examples 1 to 18
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 18 was used instead of compound 1 in experimental example 1-1.
Comparative examples 1 to 1 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 1 was used instead of compound 1 in experimental example 1-1.
Figure BDA0002476776540000611
Comparative examples 1 to 2
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 2 was used instead of compound 1 in experimental example 1-1.
Comparative examples 1 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that comparative compound 3 was used instead of compound 1 in experimental example 1-1.
Figure BDA0002476776540000612
The results of the following table 1 are obtained when current is supplied to the organic light emitting diode devices manufactured in experimental examples 1-1 to 1-14 and comparative examples 1-1, 1-2 and 1-3.
TABLE 1
Figure BDA0002476776540000613
/>
Figure BDA0002476776540000621
As shown in the data in table 1, it can be seen that the materials in which the electron withdrawing substituent is attached to the No. 1 position of fluorene all exhibit higher luminous efficiency, and the efficiencies are all well beyond the theoretical external quantum efficiency limit of 5% for the common fluorescent materials. While comparative examples 1-1, 1-2 and 1-3 all exhibited lower external quantum efficiencies.
It was confirmed that the compound of the formula according to the present invention can be used as a light emitting material to produce a high efficiency organic light emitting device.
Experimental example 2-1 ]
The compound prepared in the synthesis example was subjected to high purity sublimation purification by a generally known method, and then a sensitized organic light emitting device was manufactured by the following method.
Thin coating with a thickness of
Figure BDA0002476776540000631
The glass substrate of Indium Tin Oxide (ITO) was put into distilled water in which a cleaning agent was dissolved and subjected to ultrasonic washing. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed with isopropanol, acetone, and methanol solvents, and drying was performed. The substrate is then transferred to a plasma cleaner. In addition, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator. />
2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) of the following chemical formula was thermally and vacuum-set on the transparent ITO electrode thus prepared to a thickness of
Figure BDA0002476776540000632
As a hole injection layer.
Figure BDA0002476776540000633
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BDA0002476776540000634
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BDA0002476776540000635
Subsequently, it is made to be an electronThe following compounds 4,4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA) as barrier materials
Figure BDA0002476776540000636
Vacuum deposition is carried out on the hole transport layer to form an electron blocking layer.
Figure BDA0002476776540000637
Then, the compound 1 is used as a main material, C545T is used as a luminescent material, C545T is used as a doping material with the weight percentage of 20 percent, and the mixture is vacuum deposited on the exciton blocking layer with the thickness of
Figure BDA0002476776540000641
Thereby forming a light emitting layer.
Figure BDA0002476776540000642
The following electron-transporting materials 1,3, 5-tris [ (3-pyridyl) -3-phenyl ]]Benzene (TmPyPB)
Figure BDA0002476776540000643
And vacuum depositing on the light-emitting layer to form an electron transport layer. />
Figure BDA0002476776540000644
The compound lithium 8-hydroxyquinoline (Liq)
Figure BDA0002476776540000645
And metallic aluminum->
Figure BDA0002476776540000646
Sequentially deposited on the electron transport layer as an electron injection layer and a negative electrode.
Figure BDA0002476776540000647
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material Liq are kept at
Figure BDA0002476776540000648
Second to->
Figure BDA0002476776540000649
Organic functional layer material comprising hole transport layer material, electron blocking layer material, light emitting layer material, electron transport layer material, deposition rate is kept +.>
Figure BDA00024767765400006410
Second to->
Figure BDA00024767765400006411
The deposition rate of the electrode material metallic aluminium is kept +.>
Figure BDA00024767765400006413
Second to->
Figure BDA00024767765400006412
Per second, and maintains the vacuum level during deposition at 1X 10 -7 To 5X 10 -6 The support, thereby manufacturing the organic light emitting device.
Experimental example 2-2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 2 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 3 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 4
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 4 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 5
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 5 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 6
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 6 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 7
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 7 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 8
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 8 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 9
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 9 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 10 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 11
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 11 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 12
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 12 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 13
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 13 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 14
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 14 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 15
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 15 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 16
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 16 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 17
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 17 was used instead of compound 1 in experimental example 2-1.
Experimental examples 2 to 18
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 18 was used instead of compound 1 in experimental example 2-1.
Comparative example 2-1 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 1 was used instead of compound 1 in experimental example 2-1.
Figure BDA0002476776540000661
Comparative examples 2 to 2 ]
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 2 was used instead of compound 1 in experimental example 2-1.
Comparative examples 2 to 3
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that comparative compound 3 was used instead of the solid one
Figure BDA0002476776540000671
Compound 1 in test example 2-1.
The results of the following table 2 are obtained when current is supplied to the organic light emitting diode devices manufactured in experimental examples 2-1 to 2-14 and comparative examples 2-1, 2-2 and 2-3.
TABLE 2
Figure BDA0002476776540000672
Figure BDA0002476776540000681
As shown in the data in table 2, the green organic light emitting devices of experimental examples 2-1 to 2-18 of the present invention, in which the compound represented by chemical formula (1) was used as a host material for green fluorescent light emitting molecules, exhibited better performance in both current efficiency and driving voltage than the three compounds of the comparative example.
The organic light emitting device according to the above embodiment of the present invention may be applied to a display/lighting device, and other structures of which are known in the art, and will not be described in detail herein.
To sum up: the main functional elements of the thermal activation delay fluorescent material are that intramolecular interaction is realized through space nonconjugated connection, and a space charge transfer mechanism is realized through reasonably regulating and controlling a molecular structure and limiting the space rotation of an electron donating element and an electron withdrawing element in a molecule. The material has high thermal stability, high glass transition temperature and excellent luminescence property, and can be used as a material of an organic material layer of an organic light-emitting device, in particular a material of a core luminescent layer. The compound according to at least one exemplary embodiment of the present specification may realize high efficiency of thermally activated delayed fluorescence and achieve high efficiency of an organic light emitting device while realizing a low driving voltage. In particular, the compounds described in the present specification can be used as a light-emitting material and a host material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (5)

1. A thermally activated delayed fluorescence material characterized by comprising a compound represented by the following chemical formula (1):
Figure FDA0004104789340000011
ext> inext> formulaext> (ext> 1ext>)ext>,ext> theext> -ext> Gext> -ext> aext> bondext> isext> selectedext> fromext> anyext> oneext> ofext> theext> followingext>:ext>
Figure FDA0004104789340000012
R 9 And R is 14 And is any one of tert-butyl, phenyl, methyl or carbazolyl.
2. An organic light-emitting device comprising a first electrode and a second electrode disposed opposite each other, one or more organic material layers disposed between the first electrode and the second electrode, the organic material layers comprising the thermally activated delayed fluorescence material of claim 1.
3. The organic light-emitting device according to claim 2, wherein the organic material layer includes a light-emitting layer composed of one or more of a light-emitting material, a sensitizing material, and a host material, and the thermally activated delayed fluorescence material is any one or more of the light-emitting material, the sensitizing material, or the host material.
4. An organic light-emitting device according to claim 3, wherein the organic material layer further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and wherein the thermally activated delayed fluorescent material is contained in the one or more of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer.
5. A display/lighting device comprising the organic light-emitting device according to any one of claims 2 to 4.
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Citations (5)

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Publication number Priority date Publication date Assignee Title
CN107406391A (en) * 2015-09-30 2017-11-28 株式会社Lg化学 Spiro-compound and the organic illuminating element for including it
CN110698430A (en) * 2019-10-23 2020-01-17 苏州久显新材料有限公司 Thiaphenanthrone derivative, method for synthesizing the same, and electronic device containing the same
CN110698400A (en) * 2019-10-23 2020-01-17 苏州久显新材料有限公司 Phenanthridinone derivative, synthesis method thereof and electronic device containing phenanthridinone derivative
CN111056959A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device
CN111057005A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406391A (en) * 2015-09-30 2017-11-28 株式会社Lg化学 Spiro-compound and the organic illuminating element for including it
CN110698430A (en) * 2019-10-23 2020-01-17 苏州久显新材料有限公司 Thiaphenanthrone derivative, method for synthesizing the same, and electronic device containing the same
CN110698400A (en) * 2019-10-23 2020-01-17 苏州久显新材料有限公司 Phenanthridinone derivative, synthesis method thereof and electronic device containing phenanthridinone derivative
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CN111057005A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device

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