CN114315740A - 2, 4-diazaspiro fluorene derivatives and electronic devices - Google Patents
2, 4-diazaspiro fluorene derivatives and electronic devices Download PDFInfo
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Abstract
The invention relates to 2, 4-diazaspiro-fluorene derivatives and electronic devices. The 2, 4-diazaspiro-fluorene derivative has excellent film forming property and thermal stability by introducing the unique combined 2, 4-diazaspiro-fluorene derivative parent nucleus structure of biphenyl spirofluorene and D-pi-A structure, and can be used for preparing organic electroluminescent devices. The 2, 4-diazaspiro-fluorene derivative can be used as a material for forming a luminescent layer, a hole blocking layer or an electron transport layer, and can reduce the driving voltage, improve the efficiency and the brightness and prolong the service life.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and relates to a 2, 4-diazaspiro-fluorene derivative and an electronic device containing the 2, 4-diazaspiro-fluorene derivative. More particularly, the present invention relates to 2, 4-diazaspiro-fluorene derivatives suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors and organic solar cells, and electronic devices using the 2, 4-diazaspiro-fluorene derivatives.
Background
The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.
Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.
Disclosure of Invention
The 2, 4-diazaspiro-fluorene derivative has a unique mother nucleus of the 2, 4-diazaspiro-fluorene derivative with a combination of biphenyl structure spirofluorene and D-pi-A structure, has high thermal stability, chemical stability and carrier transport property, more importantly has proper singlet state, triplet state and molecular orbital energy level, and is easy to regulate and control the HOMO/LUMO energy level of the compound through reasonable material design. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced.
An object of the present invention is to provide a 2, 4-diazafluorenone derivative represented by the following general formula (I):
wherein X is a single bond, CR2O, S or not forming a bond;
R1，R2，R3each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, or NO2、N(R)2、OR、SR、C(＝O)R、P(＝O)R、Si(R)3A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
wherein R represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; substituted or unsubstituted aromatic hydrocarbon groups having 6 to 30 carbon atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
when R is1，R2，R3In the case of an aromatic hydrocarbon group or an aromatic heterocyclic group, the adjacent benzene rings may be connected to each other through a condensed ring.
Further alternatively, R1，R2，R3Each independently represents: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphosphoxy, diphenylphosphiloxy, triphenylsilyl or tetraphenylsilyl.
Further optionally, said aromatic hydrocarbon group or aromatic heterocyclic group is selected from: phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahnthracenyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4, 5, 9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, pyrrosinyl, pyrazinyl, quinoxalyl, pyryl, pyridylnyl, pyridoimidazolyl, pyrazinyl, pyrazinoyl, quinoxalyl, 1, 3-thiazolyl, pyridazinyl, pyridazinoyl, 1, pyridazinyl, pyridazinoyl, pyridazinyl, pyridazinoyl, pyridazinyl, pyrimidyl, and the like, Naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1, 2, 3-triazolyl, 1, 2, 4-triazolyl, benzotriazolyl, 1, 2, 3-oxadiazolyl, 1, 2, 4-oxadiazolyl, 1, 2, 5-oxadiazolyl, 1, 3, 4-oxadiazolyl, 1, 2, 3-thiadiazolyl, 1, 2, 4-thiadiazolyl, 1, 2, 5-thiadiazolyl, 1, 3, 4-thiadiazolyl, 1, 3, 5-triazinyl, 1, 2, 4-triazinyl, 1, 2, 3-triazinyl, tetrazolyl, 1, 2,4, 5-tetrazinyl, 1, 2, 3, 4-tetrazinyl, 1, 2, 3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl.
Further alternatively, the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
further alternatively, the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
further alternatively, the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
further alternatively, the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
it is a second object of the present invention to provide an electronic device comprising the 2, 4-diazaspiro-fluorene derivative according to the first object.
Further optionally, the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;
wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains a 2, 4-diazaspiro-fluorene derivative according to one of the above objects.
Further optionally, the at least one organic layer is a light emitting layer, a hole blocking layer, or an electron transport layer.
That is, the present invention is as defined in the above-mentioned embodiments.
ADVANTAGEOUS EFFECTS OF INVENTION
The 2, 4-diazaspiro-fluorene derivative has good film forming property and thermal stability by introducing the unique 2, 4-diazaspiro-fluorene derivative parent nucleus of the combination of the biphenyl structure spirofluorene and the D-pi-A structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole transmission layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transmission layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.
In addition, the preparation method of the 2, 4-diazaspiro-fluorene derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.
The 2, 4-diazaspiro-fluorene derivative has good application effect in electronic devices such as organic electroluminescent devices and the like, and has wide industrialization prospect.
The 2, 4-diazaspiro-fluorene derivative has excellent hole blocking capacity and excellent electron transport performance, and is stable in a thin film state. Therefore, the organic electroluminescent device having a hole blocking layer prepared using the 2, 4-diazaspiro-fluorene derivative of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, so that the maximum luminous brightness of the organic electroluminescent device is increased.
The 2, 4-diazaspiro-fluorene derivative can be used as a material for forming a luminescent layer, a hole blocking layer or an electron transport layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light emitting layer can be confined, and the possibility of recombination of holes and electrons can be further increased to obtain high luminous efficiency. In addition, the driving voltage is so low that high durability can be achieved.
Drawings
FIG. 1 is a fluorescence spectrum (PL) of materials 2-3 of examples of the present invention in a dichloromethane solution.
Fig. 2 is a structural view of an organic electroluminescent device according to the present invention.
Description of the reference numerals
1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-electron barrier layer, 6-luminescent layer, 7-hole barrier layer, 8-electron transport layer, 9-electron injection layer and 10-cathode.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
Example 1: synthesis of Compound 1-1
The synthetic route for intermediate M1 is shown below:
to a dry, clean, 250mL three-necked flask, 1-bromo-8-phenylnaphthalene (2.5g, 8.9mmol) and 150mL anhydrous tetrahydrofuran were added under nitrogen and dissolved with stirring at room temperature. The system was cooled to-78 ℃ and 3.9mL (2.5M, 9.8mmol) of n-butyllithium were added dropwise at this temperature and stirring continued at this temperature for 1.5 h. 3- (4-bromophenyl) -2, 4-diazafluorenone (2.7g, 8.1mmol) was then added in one portion, the bath was removed after addition, the reaction warmed to room temperature by itself and stirring was continued overnight. And after the reaction is finished, washing with water, drying and spin-drying to obtain a white solid.
The white solid was transferred to a 250mL single-neck flask equipped with a reflux condenser, 100mL of acetic acid was added, 10mL of concentrated hydrochloric acid was added dropwise with stirring, and the mixture was heated under reflux for 12 hours. After the reaction, the heating was turned off, the reaction solution was cooled to room temperature, poured into ice water, and filtered to obtain a pale yellow solid. The crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 3: 1(V/V)) to give a white solid2.9g of a colored solid, yield 68%. Ms (ei): m/z: 523.10[ M ]+]。Anal.calcd for C33H19BrN2(％)：C 75.72，H 3.66，N 5.35；found：C 75.70，H 3.68，N 5.34。
The synthetic route for compound 1-1 is shown below:
under nitrogen protection, intermediate M1(2.6g, 5mmol), bis (4-biphenylyl) amine (1.7g, 5.2mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, and the organic layers were combined. After evaporation of the solvent, the residue was isolated by column chromatography (petroleum ether: dichloromethane: 3: 1 (V/V)). The solvent was distilled off, and after drying, 2.8g of a green solid was obtained in a yield of 73%. Ms (ei): m/z: 763.78[ M ]+]。Anal.calcd for C57H37N3(％)：C 89.62，H 4.88，N 5.50；found：C 89.61，H 4.90，N 5.48。
Example 2: synthesis of Compounds 2-3
The synthetic route for compounds 2-3 is shown below:
under nitrogen protection, intermediate M1(2.6g, 5mmol), 5, 7-dihydro-7, 7-dimethyl-indeno [2, 1-B ] were added sequentially in a 250mL Schlenk flask]Carbazole (1.4g, 5mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After the reaction, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride, washed with water, the organic layer was separated, and the aqueous layer was extracted with 15mL of methylene chlorideTwo times of extraction were carried out, and the organic layers were combined. After evaporation of the solvent, the residue was isolated by column chromatography (petroleum ether: dichloromethane: 3: 1 (V/V)). The solvent was evaporated and dried to give 2.5g of a green solid in 68% yield. Ms (ei): m/z: 725.28[ M ]+]。Anal.calcd for C54H35N3(％)：C 89.35，H 4.86，N 5.79；found：C 89.30，H 4.80，N 5.76。
Example 3: synthesis of Compound 3-3
The synthetic route for compound 3-3 is shown below:
under nitrogen protection, intermediate M1(2.6g, 5mmol), M2(3.2g, 5.2mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol), and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, and the organic layers were combined. After evaporation of the solvent, the residue was isolated by column chromatography (petroleum ether: dichloromethane: 4: 1 (V/V)). The solvent was evaporated and dried to give 3.5g of a green solid in 65% yield. Ms (ei): m/z: 1065.40[ M ]+]。Anal.calcd for C78H59N5(％)：C 87.86，H 5.58，N 6.57；found：C 87.80，H 5.50，N 6.55。
Example 4: synthesis of Compound 4-1
The synthetic route of compound 4-1 is shown below:
under nitrogen protection, intermediate M1(2.6g, 5mmol), M3(1.7g, 5.2mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol), and 120mL were added sequentially in a 250mL Schlenk flaskToluene, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of dichloromethane, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of dichloromethane, and the organic layers were combined. After evaporation of the solvent, the residue was isolated by column chromatography (petroleum ether: dichloromethane: 3: 1 (V/V)). The solvent was evaporated and dried to give 2.3g of a green solid with a yield of 60%. Ms (ei): m/z: 777.28[ M ]+]。Anal.calcd for C57H35N3O(％)：C 88.01，H 4.54，N 5.40；found：C 87.98，H 4.52，N 5.40。
< organic electroluminescent device >
The organic electroluminescent device of the present invention comprises: the organic electroluminescent device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes a 2, 4-diazaspiro-fluorene derivative of the present invention.
Fig. 2 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 2, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.
The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially provided on the substrate 1.
The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above organic layer contains the compound represented by the above general formula (I). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic electroluminescent device according to the present invention may be formed by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
In the hole injection layer of the organic electroluminescent element of the present invention, a known material having a hole injection property can be used.
As the hole transport layer of the organic electroluminescent device of the present invention, a material having a hole transporting property is preferably used.
In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.
As the electron blocking layer of the organic electroluminescent device of the present invention, it is preferably formed using a known compound having an electron blocking effect.
As the light-emitting layer of the organic electroluminescent device of the present invention, a compound containing the 2, 4-diazaspiro-fluorene derivative of the present invention is preferably used. In addition to this, Alq can also be used3Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.
The light emitting layer may be composed of a host material and a dopant material. As the host material, a compound containing the 2, 4-diazaspiro-fluorene derivative of the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.
As the doping material, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the hole blocking layer of the organic electroluminescent device of the present invention, a compound containing the 2, 4-diazaspiro-fluorene derivative of the present invention is preferably used. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4, 6-tris (3-phenyl) -1, 3, 5-triazine (T2T), 1, 3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), Bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films.
The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.
As the electron transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the 2, 4-diazaspiro-fluorene derivative of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For exampleAlq may be used3Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)2) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films.
As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used.
In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.
< characterization of Material Properties >
Industrial applicability
The 2, 4-diazaspiro-fluorene derivative has excellent luminous efficiency, life characteristics and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.
The invention is illustrated by the above examples of materials and their applications, but the invention is not limited to the above examples, i.e. it is not intended that the invention must be implemented in reliance on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A2, 4-diazaspiro-fluorene derivative represented by the following general formula (I):
wherein X is a single bond, CR2O, S or not forming a bond;
R1，R2，R3each independently represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, or NO2、N(R)2、OR、SR、C(＝O)R、P(＝O)R、Si(R)3A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
wherein R represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; substituted or unsubstituted alkenyl having 2 to 20 carbon atoms; substituted or unsubstituted aromatic hydrocarbon groups having 6 to 30 carbon atoms; or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms;
when R is1，R2，R3In the case of an aromatic hydrocarbon group or an aromatic heterocyclic group, the adjacent benzene rings may be connected to each other through a condensed ring.
2. The 2, 4-diazaspiro-fluorene derivative according to claim 1,R1，R2，R3each independently represents: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphosphoxy, diphenylphosphiloxy, triphenylsilyl or tetraphenylsilyl.
3. The 2, 4-diazaspiro-fluorene derivative according to claim 1, wherein the aromatic hydrocarbon group or aromatic heterocyclic group is selected from the group consisting of: phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahnthracenyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4, 5, 9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, pyrrosinyl, pyrazinyl, quinoxalyl, pyryl, pyridylnyl, pyridoimidazolyl, pyrazinyl, pyrazinoyl, quinoxalyl, 1, 3-thiazolyl, pyridazinyl, pyridazinoyl, 1, pyridazinyl, pyridazinoyl, pyridazinyl, pyridazinoyl, pyridazinyl, pyrimidyl, and the like, Naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1, 2, 3-triazolyl, 1, 2, 4-triazolyl, benzotriazolyl, 1, 2, 3-oxadiazolyl, 1, 2, 4-oxadiazolyl, 1, 2, 5-oxadiazolyl, 1, 3, 4-oxadiazolyl, 1, 2, 3-thiadiazolyl, 1, 2, 4-thiadiazolyl, 1, 2, 5-thiadiazolyl, 1, 3, 4-thiadiazolyl, 1, 3, 5-triazinyl, 1, 2, 4-triazinyl, 1, 2, 3-triazinyl, tetrazolyl, 1, 2,4, 5-tetrazinyl, 1, 2, 3, 4-tetrazinyl, 1, 2, 3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl.
4. The 2, 4-diazaspiro-fluorene derivative according to claim 1, wherein the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
5. the 2, 4-diazaspiro-fluorene derivative according to claim 1, wherein the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
6. the 2, 4-diazaspiro-fluorene derivative according to claim 1, wherein the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
7. the 2, 4-diazaspiro-fluorene derivative according to claim 1, wherein the 2, 4-diazaspiro-fluorene derivative represented by the general formula (I) is selected from the following compounds:
8. an electronic device comprising the 2, 4-diazaspiro-fluorene derivative according to any one of claims 1 to 7.
9. The electronic device according to claim 8, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;
wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the 2, 4-diazaspiro-fluorene derivative according to any one of claims 1 to 8.
10. The electronic device of claim 8, wherein the at least one organic layer is a light emitting layer, a hole blocking layer, or an electron transport layer.
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