CN111848493B - Derivative containing spirobifluorene and organic electroluminescent device thereof - Google Patents
Derivative containing spirobifluorene and organic electroluminescent device thereof Download PDFInfo
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Abstract
The invention provides a spirobifluorene-containing derivative and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The invention aims to solve the technical problems that the hole transport material in the existing organic electroluminescent device has poor stability and the service life of the organic electroluminescent device is short. The spirobifluorene-containing derivative takes spirobifluorene groups as a matrix and is connected with carbazole-indene groups through single bonds or bridges. The organic electroluminescent device of the present invention includes an anode, an organic layer, and a cathode, the organic layer including a hole transport layer. The derivative containing spirobifluorene in the formula I has a more suitable HOMO energy level and better stability, and when the derivative is used for a hole transport layer of an organic electroluminescent device, the organic electroluminescent device has higher luminous efficiency, lower driving voltage and longer service life.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a spirobifluorene-containing derivative and an organic electroluminescent device thereof.
Background
An Organic Light-Emitting Diode (OLED) is a solid-state device composed of Organic molecular sheets, which can emit Light when power is applied. The OLED is called a fantasy display technology because of its high efficiency, high contrast, large viewing angle, fast response time, saturated colors, and relatively simple structure, and has a very wide application prospect in display and illumination. Since OLEDs can be fabricated on a variety of different substrates, they are a key technology for flexible displays. The OLED device is composed of an n-type functional layer, a p-type functional layer, a light emitting layer, a cathode and an anode. The n-type functional Layer includes a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), and the like, and the p-type functional Layer includes a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and the like.
OLED devices can be divided into two broad categories, depending on the organic functional material used: small molecule devices and high molecule devices. Small molecule OLED technology has advanced earlier and has reached the level of commercial production. The development of high-molecular OLEDs, also called POLEDs, started in 1990, and it is possible to greatly reduce the device production cost because the polymer can be made into thin films by spin coating, inkjet printing, etc., but the technology is far from mature. The OLED device may be classified into a passive driving type and an active driving type according to a driving method. A passive drive type does not use a Thin Film Transistor (TFT) substrate, and is generally suitable for medium and small size display; the active drive type uses a TFT substrate, and is suitable for medium and large size display, especially large size full color dynamic image display. Currently, the technologies of the passive driving type OLED and the active driving type OLED are well developed, and a large number of commercial products have been introduced.
For an organic electroluminescent device with an ITO glass transparent electrode as an anode, opaque metal as a cathode, and an electron transport layer, a luminescent layer and a hole transport layer as organic functional layers, under the drive of a certain voltage, electrons and holes are respectively injected from the cathode and the anode into the electron and hole transport layers and then respectively migrate to the luminescent layer, the electrons and the holes meet to form excitons so as to excite luminescent molecules, and the latter emits visible light after radiation. The radiated light can be observed from the ITO side, and the metal electrode film also functions as a reflective layer.
OLED devices require that holes injected from the anode and electrons injected from the cathode be injected into the light-emitting layer in a relatively balanced manner, i.e. that the injection rates of holes and electrons should be substantially the same. The hole transport layer is adjacent to the light emitting layer, and plays a crucial role in the OLED device, reducing the driving voltage and improving the light emitting efficiency, so that it is necessary to select a suitable hole transport material when preparing the OLED device. Compared with electron transport materials and light emitting materials, the hole transport materials have lower stability, which can cause the performance attenuation of the OLED device, and thus become a main factor influencing the performance, particularly the service life, of the organic electroluminescent device, and therefore, the improvement of the stability of the hole transport materials is a focus of research.
Disclosure of Invention
The invention provides a spirobifluorene-containing derivative and an organic electroluminescent device thereof, aiming at solving the problems of poor material stability of an organic functional layer in the conventional organic electroluminescent device, particularly poor stability of a hole transport material and short service life of the organic electroluminescent device.
The present invention has been accomplished by the above-mentioned object achieved by using a spirobifluorene derivative represented by the following formula I as an organic functional layer material of an organic electroluminescent device.
The invention provides a spirobifluorene-containing derivative which has a structural general formula shown in a formula I,
ar is selected from one of the groups shown in the specification,
wherein, X is 1 、X 2 Independently selected from a single bond or C (R) 0 ) 2 And X 1 、X 2 Not simultaneously being a single bond, R 0 One selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
m is an integer from 0 to 4, n is an integer from 0 to 3, k is an integer from 0 to 2, R is one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C30 alkyl, and each R is the same or different;
the L is selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group;
ar is 0 Selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstitutedAnd (3) one of C6 to C30 aryl groups.
The invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer contains the spirobifluorene-containing derivative.
Has the advantages that: the derivative containing spirobifluorene in the formula I has a proper HOMO energy level, and can effectively inject holes into a light-emitting layer, so that more excitons are generated in the light-emitting layer to emit light, the light-emitting efficiency of the device is effectively improved, and the HOMO energy level of the derivative is more matched with an anode and the light-emitting layer, so that the injection barrier of the holes is lower, and the driving voltage of the device using the derivative containing spirobifluorene in the formula I as a hole transport layer is lower. In addition, the spirobifluorene-containing derivative of the formula I has better stability, an organic film containing the derivative of the formula I is not easy to deform during the operation of a device, and the service life of an organic electroluminescent device is effectively prolonged.
Drawings
FIG. 1 is a drawing showing Compound 1 of the present invention 1 H NMR chart; FIG. 2 shows Compound 12 of the present invention 1 H NMR chart;
FIG. 3 is a photograph of Compound 184 of the present invention 1 H NMR chart; FIG. 4 shows a scheme for preparing a compound 194 of the invention 1 H NMR chart;
FIG. 5 is a drawing of Compound 215 of the present invention 1 H NMR chart; FIG. 6 shows a schematic representation of compound 225 of the present invention 1 H NMR chart;
FIG. 7 shows Compound 232 of the present invention 1 H NMR chart; FIG. 8 is a drawing of Compound 240 of the present invention 1 H NMR chart.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.
The hydrogen (H) according to the invention comprises the isotopes protium (P), deuterium (D) and tritium (T).
The alkyl refers to a univalent group formed by subtracting one hydrogen atom from an alkane molecule, and the alkyl is a saturated hydrocarbon group without any double bond or triple bond. The alkyl group includes straight chain alkyl, branched chain alkyl and cycloalkyl. The alkyl group has 1 to 60 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl (including isomers thereof), butyl (including isomers thereof), pentyl (including isomers thereof), hexyl (including isomers thereof), heptyl (including isomers thereof), octyl (including isomers thereof), nonyl (including isomers thereof), decyl (including isomers thereof), undecyl (including isomers thereof), dodecyl (including isomers thereof), tridecyl (including isomers thereof), tetradecyl (including isomers thereof), pentadecyl (including isomers thereof), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornanyl, norbornyl and the like. Examples of isomers of the above alkyl groups are as follows, propyl groups include n-propyl groups, isopropyl groups, butyl groups include n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, and the like.
The aryl group in the invention is a univalent group formed by subtracting one hydrogen atom from an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl group, polycyclic aryl group, condensed ring aryl group. The aryl group has a carbon number of C6 to C60, preferably C6 to C30, more preferably C6 to C20, and still more preferably C6 to C14. Examples of the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, anthracyl, triphenylene, pyrenyl, perylenyl, fluoranthenyl, indenyl, fluorenyl, benzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, and the like.
The heteroaryl group in the present invention refers to a monovalent group in which at least one carbon atom in the aryl group is substituted with a heteroatom. The hetero atom includes, but is not limited to, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a boron atom, a phosphorus atom, and the like as shown below. The heteroaryl includes monocyclic heteroaryl, polycyclic heteroaryl, fused ring heteroaryl. The heteroaryl group has a carbon number of C3 to C60, preferably C3 to C30, more preferably C3 to C20, and still more preferably C3 to C10. Examples of such heteroaryl groups include, but are not limited to, furyl, benzofuryl, dibenzofuryl, benzodibenzofuryl, thienyl, benzothienyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, naphthyridinyl, and the like.
The arylene group in the present invention is a divalent group formed by subtracting two hydrogen atoms from an aromatic hydrocarbon molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused ring arylene, or combinations thereof. The arylene group has a carbon number of C6 to C60, preferably C6 to C30, more preferably C6 to C20, and still more preferably C6 to C14. Examples of the arylene group include, but are not limited to, phenylene, biphenylene, terphenylene, quaterphenylene, naphthylene, phenanthrylene, anthracenylene, triphenylene, pyrenylene, fluorenylene, benzofluorenylene, spirobifluorenylene, benzospirobifluorenylene and the like.
The heteroarylene group refers to a divalent group in which at least one carbon atom in the arylene group is substituted with a heteroatom. The hetero atom includes, but is not limited to, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a boron atom, a phosphorus atom, and the like as shown below. The heteroarylene group includes a monocyclic heteroarylene group, a polycyclic heteroarylene group, a fused ring heteroarylene group, or a combination thereof. The heteroarylene group has from C3 to C60, preferably from C3 to C30, more preferably from C3 to C20, and still more preferably from C3 to C10. Examples of the heteroarylene group include, but are not limited to, a furanylene group, a benzofuranylene group, a dibenzofuranylene group, a thiophenylene group, a benzothiophene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, a pyridinylene group, a pyrimidinylene group, a pyrazinylene group, a triazinylene group, a quinolylene group, an isoquinolylene group and the like.
The "C6 to C30" in the "substituted or unsubstituted C6 to C30 aryl" means the number of carbon atoms in the unsubstituted "aryl" and does not include the number of carbon atoms in the substituent. The "C3 to C30" in the "substituted or unsubstituted C3 to C30 heteroaryl" represents the number of carbon atoms in the unsubstituted "heteroaryl", and does not include the number of carbon atoms in the substituent. The "C1 to C30" in the "substituted or unsubstituted C1 to C30 alkyl group" represents the number of carbon atoms in the unsubstituted "alkyl group" and does not include the number of carbon atoms in the substituent. Other cases are not described in detail, and so on.
The term "unsubstituted" in the "substituted or unsubstituted" as used herein means that a hydrogen atom on the group is not replaced by any substituent.
The term "substituted" in the "substituted or unsubstituted" as used herein means that at least one hydrogen atom on the group is replaced by a substituent. When a plurality of hydrogens is replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted by the substituent may be any position.
The substituent group represented by the "substituted" in the above "substituted or unsubstituted" is selected from one of deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl. Preferably deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted heptyl group, a substituted or unsubstituted octyl group, a substituted or unsubstituted nonyl group, a substituted or unsubstituted decyl group, a substituted or unsubstituted undecyl group, a substituted or unsubstituted dodecyl group, a substituted or unsubstituted tridecyl group, a substituted or unsubstituted tetradecyl group, a substituted or unsubstituted pentadecyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted bornyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted quinoxalinyl group, or substituted or unsubstituted quinoxalinyl group.
The term "integer selected from 0 to M" as used herein means any one of the values selected from integers from 0 to M, including 0,1,2 … M-2,M-1,M. For example, "m is selected from an integer of 0 to 4" means that m is selected from 1,2,3,4; "n is an integer selected from 0 to 3" means that n is selected from 0,1,2,3; and so on.
The invention provides a spirobifluorene-containing derivative which has a structural general formula shown in a formula I,
ar is selected from one of the groups shown in the specification,
wherein, X is 1 、X 2 Independently selected from a single bond or C (R) 0 ) 2 And X 1 、X 2 Not simultaneously being a single bond, R 0 One selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
m is an integer from 0 to 4, n is an integer from 0 to 3, k is an integer from 0 to 2, R is one selected from hydrogen, deuterium, and substituted or unsubstituted C1-C30 alkyl, and each R is the same or different;
the L is selected from one of a single bond, a substituted or unsubstituted C6-C30 arylene group and a substituted or unsubstituted C3-C30 heteroarylene group;
ar is 0 And one selected from substituted or unsubstituted C1-C30 alkyl and substituted or unsubstituted C6-C30 aryl.
Preferably, the spirobifluorene-containing derivative has a structural general formula shown in I-1-I-6,
ar is 0 Is selected from one of the groups shown below,
p is selected from an integer of 0 to 5, q is selected from an integer of 0 to 7, m is selected from an integer of 0 to 4, R 1 One selected from hydrogen, deuterium, and substituted or unsubstituted alkyl groups of 1 to 30, each R 1 The same or different.
Preferably, the R is one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted heptyl group, a substituted or unsubstituted octyl group, a substituted or unsubstituted nonyl group, a substituted or unsubstituted decyl group, a substituted or unsubstituted undecyl group, a substituted or unsubstituted dodecyl group, a substituted or unsubstituted tridecyl group, a substituted or unsubstituted tetradecyl group, and a substituted or unsubstituted pentadecyl group.
Preferably, the L is selected from a single bond or one of the groups shown below,
the X is selected from O, S, N (Rx), C (Rx) 2 Rx is selected from one of substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C30 aryl; said L 1 、L 2 Independently selected from a single bond or substituted or unsubstituted phenylene.
Preferably, ar is 0 Selected from one of the following groups,
preferably, the L is selected from a single bond or one of the groups shown below,
preferably, the spirobifluorene-containing derivative of formula I is selected from one of the structures shown in the following,
some specific chemical structures of the spirobifluorene-containing derivative shown in formula I are listed above, but the invention is not limited to the listed chemical structures, and all the derivatives are based on the structure shown in formula I, and the substituent groups are defined as above.
The invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer contains the spirobifluorene-containing derivative.
Preferably, the organic layer includes a hole transport layer containing the spirobifluorene-containing derivative of the present invention described above.
The organic layer of the present invention may further include one or more of a hole injection layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like, in addition to the hole transport layer. Functional layers other than the organic layer, for example, functional layers located outside the anode or the cathode, may also be included.
The structure of the organic electroluminescent device of the present invention may be of several types as shown below, but is not limited to the limited structures listed:
anode/hole transport layer/light emitting layer/cathode
Anode/hole transport layer/light emitting layer/electron transport layer/cathode
Anode/hole transport layer/electron blocking layer/light emitting layer/cathode
Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode
Anode/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode
Anode/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/cathode
Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
Electrode material
In order to effectively inject, transmit and compound carriers in a device to emit light, the electrode material has good conductivity and stable chemical properties; has a suitable work function to reduce the injection barrier; finally, the electrode also needs to have higher transparency in the visible light range as a light extraction electrode.
Anode material: the invention is as describedThe anode material of (2) is preferably a material having a high work function in order to improve the hole injection efficiency. The anode material includes, but is not limited to, a metal oxide, a metal alloy, and the like. Examples of the anode material include, but are not limited to, silver (Ag), aluminum (Al), platinum (Pt), indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide aluminum (ZnO: al), or tin oxide antimony (SnO) 2 Sb), and the like.
Cathode material: the cathode material according to the present invention is preferably a material having a low work function in order to improve the electron injection efficiency. The cathode material includes, but is not limited to, metals, metal alloys, and the like. Examples of the cathode material include, but are not limited to, aluminum (Al), silver (Ag), gold (Au), lead (Pb), magnesium-silver alloy (Mg: al), lithium-aluminum alloy (Li: al), lithium-calcium-magnesium alloy (Li: ca: mg), and the like.
Infusion material
Hole injection material: the hole injection material of the present invention is preferably a material that can effectively reduce the interfacial barrier between the anode and the hole transport layer. The hole injection material includes an organic hole injection material and an inorganic hole injection material. The organic hole injection material includes, but is not limited to, low molecular organic compounds such as phthalocyanine compounds, arylamine compounds, and polycyano-containing conjugated organic materials, and high molecular materials; examples of the organic hole injection material include, but are not limited to, copper phthalocyanine (CuPc), N4 '-tetrakis (4-methoxyphenyl) - [1,1' -biphenyl]-4,4' -diamine (MeO-TPD), 1,4,5,8,9,11-hexaazabenzonitrile (HAT-CN), 2,3,5,6-tetrafluoro-7,7 ',8,8' -tetracyanoquinodimethane (F4-TCNQ), poly (N-vinylcarbazole) (PVK), poly (3,4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (PEDOT/PSS), and the like. The inorganic hole injecting material includes, but is not limited to, metal oxides, metal halides, and the like; examples of the inorganic hole injection material include, but are not limited to, a material described below, molybdenum trioxide (MoO) 3 ) Silver oxide (AgO), vanadium pentoxide (V) 2 O 5 ) Tungsten trioxide (WO) 3 ) Nickel oxide (NiO), titanium dioxide (TiO) 2 ) Iron trichloride (FeCl) 3) And the like.
Electron injection material: the electron injection material of the present invention is preferably a material capable of effectively reducing the interfacial barrier between the cathode and the electron injection layer. The electron injecting material includes, but is not limited to, alkali metal oxides, alkali metal fluorides, alkali metal salts, and the like. Examples of the electron injecting material include, but are not limited to, materials shown below, lithium oxide (Li) 2 O), lithium boron oxide (LiBO) 2 ) Lithium fluoride (LiF), sodium fluoride (NaF), cesium fluoride (CsF), lithium 8-hydroxyquinoline (Liq), potassium siloxide (K) 2 SiO 3 ) Cesium carbonate (Cs) 2 CO 3 ) Rubidium acetate (CH) 3 COORb) and the like.
Transport material
Hole transport material: the hole transport material of the present invention is preferably a material having a high hole mobility and a good stability. The hole transport material is preferably a spirobifluorene-containing derivative of the formula I according to the invention.
Electron transport material: the electron transport material of the present invention is preferably a material having high electron mobility, appropriate electron energy level, and good stability. The electron transport material includes a metal complex, a phenanthroline derivative, an imidazole derivative, a pyridine derivative, and the like, but is not limited thereto. Examples of the electron transport material include, but are not limited to, a material described below, tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 4,7 diphenyl-1,10 phenanthroline (Bphen), 1,3,5 tris (N-phenyl-2-benzimidazole) benzene (TPBi), 3,3'- [5' - [3- (3-pyridyl) phenyl ] benzene (TPBi)](abbreviated as TmPyPB).
Barrier material
Electron blocking material: the electron blocking layer of the present invention is preferably a material having a high LUMO level and a high hole mobility. The electron blocking material of the present invention includes triarylamine derivatives, diamine derivatives, and the like, but is not limited thereto. Examples of electron transport materials of the present invention include, but are not limited to, the materials 4,4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4,4 ' -diamine (NPB), and the like.
Hole blocking material: the hole blocking layer of the present invention is preferably a material having a lower HOMO level and a higher electron mobility. The hole blocking material of the present invention includes imidazole derivatives, phenanthroline derivatives, metal complexes, and the like, but is not limited thereto. Examples of the hole blocking layer of the present invention include, but are not limited to, materials such as 1,3,5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-bis (naphthalene-2-yl) -4,7-diphenyl-1,10-phenanthroline (NBphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), bis (8-hydroxy-2-methylquinoline) - (4-phenylphenoxy) aluminum (BAlq), and the like.
Luminescent material
The luminescent material of the present invention can be classified into a fluorescent material and a phosphorescent material according to a luminescent mechanism, and can be classified into a red luminescent material, a green luminescent material and a blue luminescent material according to luminescent colors.
Fluorescent material: the fluorescent material of the method comprises a red fluorescent material, a green fluorescent material and a blue fluorescent material. The red fluorescent material of the present invention includes, but is not limited to, DCM series materials and the like. Examples of the red fluorescent material include, but are not limited to, 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), 4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-9-enyl) -4H-pyran (DCJTB), and the like. The green fluorescent material of the present invention includes a metal complex, coumarin dye, and the like, but is not limited thereto. Examples of the green fluorescent material include, but are not limited to, a material described below, tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) Coumarin 545T (C-525T) and the like. The blue fluorescent material includes anthracene derivatives, fluorene derivatives, perylene derivatives, styrylamine derivatives, and the like, but is not limited thereto. Examples of the blue fluorescent material include, but are not limited to, materials as described below, 9,10-di- (2-naphthyl) Anthracene (ADN), 9- [4- (2- (7- (N, N-diphenylamino) -9,9-diethylfluoren-2-yl) vinyl) phenyl]-9-phenyl-fluorene (DPAFVF), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), and the like.
Phosphorescent material: the phosphorescent material comprises red phosphorescent material, green phosphorescent material and blue phosphorescent materialA material. The red phosphorescent material of the present invention includes metal complexes such as iridium complexes, platinum complexes, europium complexes, etc., but is not limited thereto. Examples of the red phosphorescent material of the present invention include, but are not limited to, materials described below, bis (1-phenylisoquinoline) (acetylacetone) iridium (III) (Ir (piq) 2 (acac), platinum octaethylporphyrin (PtOEP), tris (dibenzoylmethane) mono (phenanthroline) europium (III) (Eu (dbm) 3 (Phen)), etc., but is not limited thereto. The green phosphorescent material of the present invention includes metal complexes such as aluminum complexes, iridium complexes, zinc complexes, and the like, but is not limited thereto. Examples of the green phosphorescent material of the present invention include, but are not limited to, a material described below, tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) Tris (2-phenylpyridine) iridium (Ir (ppy) 3 ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) 2 (acac)), bis [2- (2-benzothiazolyl) phenol]Zinc (Zn (BTZ) 2 ) And the like, but are not limited thereto. The blue phosphorescent material provided by the invention comprises metal complexes such as iridium complex and beryllium complex, but is not limited to the metal complexes. Examples of blue phosphorescent materials of the present invention include, but are not limited to, materials shown below, iridium bis (4,6-difluorophenylpyridine-C2, N) picolinate (FIrpic), iridium bis (2,4-difluorophenylpyridine) -tetrakis (1-pyrazolyl) borate (Fir 6), beryllium bis (2-hydroxyphenylpyridine) (Bepp) 2 ) And the like, but are not limited thereto.
The fluorescent material and the phosphorescent material may be used alone in the light-emitting layer, or may be used as a guest material together with a host material in the light-emitting layer. When a fluorescent material or a phosphorescent material is used in the light-emitting layer together with a host material, the host material is preferably a material having a higher lowest unoccupied orbital level and a lower highest occupied orbital level than the guest material. The host material includes a metal complex, a fluorene derivative, an anthracene derivative, a carbazole derivative, and the like, but is not limited thereto. Examples of such host materials include, but are not limited to, the material tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 2,7-bis [9,9-bis (4-methylphenyl) -fluoren-2-yl]-9,9-bis (4-methylphenyl) fluorene (TDAF), 9,10-bis (2-naphthyl) Anthracene (ADN), 1,3,5-tris (9-carbazolyl) benzene (TCP), 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), and the like.
The anode, the cathode, the hole injection layer, the electron injection layer, the hole transport layer, the electron transport layer, the hole blocking layer, the electron blocking layer, the light emitting layer, and the like of the present invention may have a single-layer structure or a stacked-layer structure. When in a laminate structure, the films may be the same or different. Each layer may be a film structure formed of a single material or a film structure formed of a mixture of a plurality of materials. The thickness of the anode is 10nm to 1 μm, preferably 50nm to 500nm, and more preferably 50nm to 200nm. The thickness of the cathode is 0.1nm to 1 μm, preferably 5nm to 500nm, and more preferably 5nm to 200nm. The film thickness of the hole injection layer is 0.1nm to 500nm, preferably 1nm to 200nm, and more preferably 5nm to 100nm. The thickness of the electron injection layer is 0.001 to 500nm, preferably 0.01 to 200nm, and more preferably 0.1 to 100nm. The film thickness of the hole transport layer is preferably 5nm to 800nm, preferably 10nm to 500nm, and more preferably 10nm to 200nm. The thickness of the electron transport layer is 1nm to 500nm, preferably 5nm to 200nm, and more preferably 5nm to 100nm. The film thickness of the hole blocking layer is 0.1nm to 200nm, preferably 1nm to 100nm, and more preferably 5nm to 100nm. The thickness of the electron blocking layer is 0.1nm to 200nm, preferably 1nm to 100nm, and more preferably 5nm to 100nm. The thickness of the light-emitting layer is 5nm to 400nm, preferably 10nm to 200nm, and more preferably 10nm to 100nm.
The method for preparing each layer of thin film in the organic electroluminescent device of the present invention is not particularly limited, and vacuum evaporation, sputtering, spin coating, spray coating, screen printing, laser transfer printing, and the like may be used, but is not limited thereto.
The organic electroluminescent device of the invention mainly has two application fields, namely information display and solid illumination. The display device is widely applied to various information displays in the aspect of information display, such as tablet computers, flat televisions, mobile phones, smart watches, digital cameras, VR, vehicle-mounted systems, wearable devices and the like.
Synthetic examples
The method for preparing the spirobifluorene-containing derivative represented by formula I of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be employed. For example, bromination, cyclization, carbon-carbon coupling, and the like.
For example, the spirobifluorene-containing derivatives of the present invention can be prepared using the synthetic route shown below:
1.
2.
3.
4.
5.
6.
the V is selected from halogen, such as any one of Cl, br and I; w is selected from
Or
Raw materials and reagents: the starting materials and reagents used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art. The raw materials and reagents used in the invention are all pure reagents.
The instrument comprises the following steps: G2-Si quadrupole tandem time-of-flight high resolution mass spectrometry, produced by waters, uk; a Vario EL cube type organic element analyzer manufactured by Elementar corporation, germany; model Bruker-510 nuclear magnetic resonance spectrometer manufactured by Bruker, germany.
Synthesis example 1: preparation of Compound 1
To a 1L reaction flask, compound A-1 (7.08g, 25.0 mmol) and N, N-dimethylformamide (600 ml) were added in this order, and stirring was carried out to dissolve compound A-1, followed by slowly adding N-bromosuccinimide (NBS) (4.45g, 25.0 mmol) to the reaction flask over 30 minutes at room temperature with exclusion of light, stirring the mixture for 8 hours, and then pouring into sodium carbonate solution (3M, 1.2L). The reaction solution is extracted by dichloromethane, organic phases are combined, the organic phases are dried and concentrated in turn, and finally, the compound B-1 is obtained by recrystallization by methanol. Mass 8.33g, yield 92%.
Toluene (69 ml), compound B-1 (7.97g, 22.0mmol), phenylboronic acid (3.22g, 26.4mmol), ethanol (34 ml), a potassium carbonate solution (2M, 34.0ml), tetratriphenylphosphine palladium (1.27mg, 0.0011mmol) were sequentially added to a 500ml reaction flask, and refluxed for 4 hours under nitrogen protection, after the reaction was completed, the reaction solution was cooled to room temperature, washed with water, then extracted with dichloromethane, the organic phases were combined, dried, concentrated, and recrystallized with toluene to obtain Compound C-1. 5.46g in mass, 69% in yield.
Under nitrogen protection, a 500ml reaction flask was charged with Compound C-1 (5.39g, 15.0mmol), compound D-1 (6.34g, 12.5mmol), sodium t-butoxide (3.60g, 37.5mmo)l), toluene (190 ml), dibenzylideneacetone dipalladium (57.23mg, 0.0625 mmol), and tri-tert-butylphosphine (12.65mg, 0.0625 mmol) were reacted under reflux for 24 hours, and after the reaction was completed, the reaction mixture was cooled to room temperature. The reaction was extracted with dichloromethane, the organic phases combined, the organic phase was washed successively with water, dried, filtered through celite, the filtrate was concentrated and recrystallized from ethanol to give compound 1. Mass 7.76g, yield 79%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:785.4117 (theoretical value: 785.4022). Theoretical element content (%) C 60 H 51 N: c,91.68; h,6.54; n,1.78, measured elemental content (%): c,91.86; h,6.32; n,1.82. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.38 (s, 1H), 8.34 (s, 1H), 8.17 (s, 1H), 8.09-8.00 (m, 4H), 7.98-7.90 (m, 2H), 7.82 (dd, 2H), 7.73 (d, 1H), 7.69-7.63 (m, 5H), 7.62-7.56 (m, 3H), 7.52-7.42 (m, 6H), 7.33 (t, 1H), 1.76 (s, 6H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Synthesis example 2: preparation of Compound 12
To a 500ml reaction flask were added 9,9-dimethyl-2-bromofluorene (27.3g, 100mmol), 3-amino-4-chlorophenylboronic acid pinacol (30.4g, 120mmol), sodium tert-butoxide (19.2g, 200mmol), bis (dibenzylideneacetone) palladium (1.15g, 2mmol), 2,2-bis (diphenylphosphino) -1,1-Binaphthyl (BINAP) (2.49g, 4mmol), toluene (320 ml), and stirred under nitrogen at reflux overnight. After the reaction, the reaction solution was filtered, the filtrate was concentrated, and column chromatography (silica gel, dichloromethane) was performed to obtain compound b-1. Mass 35.2g, yield 79%.
A500 ml reaction flask was charged with compound b-1 (26.7g, 60mmol), potassium carbonate (16.6g, 120mmol), palladium acetate (135mg, 0.6 mmol), tricyclohexylphosphine tetrafluoroborate (220mg, 0.6 mmol), and N, N-dimethylacetamide (280 ml) and refluxed under nitrogen overnight. After the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, the organic phases were combined, washed successively with water, dried over anhydrous magnesium sulfate, concentrated, and subjected to column chromatography (silica gel, dichloromethane: n-hexane) to obtain compound c-1. Mass 18.4g, yield 75%.
Toluene (69 ml), bromobenzene deuterium (3.56g, 22.0mmol), compound C-1 (10.8g, 26.4mmol), ethanol (34 ml), potassium carbonate solution (2M, 34.0ml), tetratriphenylphosphine palladium (1.27mg, 0.0011mmol) were sequentially added to a 500ml reaction flask, and after the reaction was completed, the reaction solution was refluxed for 4 hours under nitrogen protection, cooled to room temperature, washed with water, then extracted with dichloromethane, combined with organic phases, dried and concentrated, and recrystallized with toluene to obtain compound C-2. 5.61g in mass, 70% in yield.
Under nitrogen protection, compound C-2 (5.47g, 15.0 mmol), compound D-1 (6.34g, 12.5 mmol), sodium tert-butoxide (3.60g, 37.5 mmol), toluene (190 ml), dibenzylideneacetone dipalladium (57.23mg, 0.0625 mmol), and tri-tert-butylphosphine (12.65mg, 0.0625 mmol) were added in this order to a 500ml reaction flask, and after completion of the reaction, the reaction mixture was cooled to room temperature. The reaction solution was extracted with dichloromethane, the organic phases were combined, the organic phase was washed with water, dried, filtered through celite in succession, the filtrate was concentrated and recrystallized from ethanol to give compound 12. Mass 7.12g, yield 72%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:790.4429 (theoretical value: 790.4335). Theoretical element content (%) C 60 H 46 D 5 N: c,91.10; h,7.13; n,1.77, measured elemental content (%): c,91.26; h,7.25; n,1.49. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.20 (d, 1H), 8.03 (d, 1H), 7.98 (d, 1H), 7.90-7.85 (m, 2H), 7.77-7.71 (m, 5H), 7.67 (s, 1H), 7.63 (d, 1H), 7.57-7.52 (m, 2H), 7.51-7.46 (m, 5H), 7.41-7.37 (m, 1H), 7.33-7.29 (m, 2H), 1.72 (s, 6H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Synthetic example 3: preparation of Compound 31
A250 ml reaction vessel was charged with the compound C-1 (5.39g, 15mmol), 4-bromobenzeneboronic acid (3.61g, 18mmol), potassium phosphate (9.55g, 45mmol), cuprous iodide (1.43g, 7.5mmol), ethylenediamine (1.00ml, 15mmol) and toluene (150 ml) in this order, and reacted under reflux for 12 hours. After the reaction, ethyl acetate is used for extraction, organic phases are combined, and the organic phases are washed by water, dried, concentrated and recrystallized by toluene to obtain the compound E-1. Mass 4.67g, yield 65%.
A reaction flask was charged with compound E-1 (4.31g, 9mmol), compound D-1 (3.81g, 7.5mmol), toluene (75 ml), ethanol (18.72 ml), potassium carbonate solution (7.5ml, 2M), and tetratriphenylphosphine palladium (43.3mg, 0.0375mmol) in this order, and refluxed under nitrogen for 7 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into cold water and extracted with dichloromethane, and the organic phases were combined, dried, concentrated, and subjected to column chromatography (silica gel, dichloromethane: petroleum ether = 2:1) to obtain compound 31. Mass 5.56g, yield 86%. The purity of the solid is not less than 99.9% by HPLC. Mass spectrum m/z:861.4424 (theoretical value: 861.4335). Theoretical element content (%) C 66 H 55 N: c,91.95; h,6.43; n,1.62, measured elemental content (%): c,91.86; h,6.53; n,1.61. The above results confirmed that the obtained product was the objective product.
Synthetic example 4: preparation of Compound 53
Compound 53 was obtained in the same manner as in the other steps except that compound D-1 in Synthesis example 1 was replaced with equimolar compound D-2. Mass 8.00g, yield 76%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:841.4731 (theoretical value: 841.4648). Theoretical element content (%) C 64 H 59 N: c,91.28; h,7.06; n,1.66, measured elemental content (%): c,91.45; h,7.01; n,1.54. The above results confirmed that the obtained product was the objective product.
Synthesis example 5: preparation of Compound 80
Compound D-1 in Synthesis example 1 was replaced with equimolar compound D-3, and the other steps were carried out in the same manner to give compound 80. Mass 6.71g, yield 78%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:687.3017 (theoretical value: 687.2926). Theoretical element content (%) C 53 H 37 N: c,92.54; h,5.42; n,2.04, measured elemental content (%): c,92.63; h,5.31; and N,2.06. The above results confirmed that the obtained product was the objective product.
Synthetic example 6: preparation of Compound 184
Synthetic example 7: preparation of Compound 194
Will be synthesized into solid9,9-dimethyl-2-bromofluorene in example 2 was changed to equimolar compound 1-bromo-9,9-dimethyl-9H-fluorene, and the other steps were the same, to give compound 194. Mass 7.37g, yield 75%. The purity of the solid is not less than 99.9% by HPLC. Mass spectrum m/z: measured value: 785.4301 (theoretical value: 785.4022). Theoretical element content (%) C 60 H 51 N: c,91.68; h,6.54; n,1.78, measured elemental content (%): c,91.72; h,6.69; n,1.59. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.28 (d, 1H), 8.20-8.17 (m, 2H), 8.06 (d, 1H), 7.99-7.91 (m, 3H), 7.84 (d, 2H), 7.81 (d, 1H), 7.75-7.62 (m, 9H), 7.60-7.56 (m, 1H), 7.51-7.46 (m, 3H), 7.44 (t, 3H), 7.35-7.31 (m, 1H), 1.66 (s, 6H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Synthesis example 8: preparation of Compound 215
4-boronic acid-9,9-dimethylfluorene (28.6g, 120.0mmol), 2-bromo-4-chloro-1-nitrobenzene (23.6g, 100.0mmol), toluene (250 ml), ethanol (80 ml), potassium carbonate solution (2M, 75ml), tetrakis (triphenylphosphine) palladium (1.16g, 1.00mmol) were added to a 1L reaction flask, and refluxed for 6 hours under nitrogen protection. After the reaction, the reaction solution was cooled to room temperature, filtered, the filtrate was extracted with chloroform, the solvent in the organic phase was evaporated, and then column chromatography (silica gel, ethyl acetate) was performed to obtain compound b-3. Mass 24.5g, yield 70%.
A500 ml reaction flask was charged with compound b-3 (21.0 g, 60mmol), triphenylphosphine (47.2g, 180mmol) and 1,2-dichlorobenzene (300 ml), and the mixture was stirred under reflux under nitrogen 1 for 10 hours. After the reaction, the reaction solution was cooled to room temperature, filtered, the filtrate was extracted with chloroform, the solvent in the organic phase was evaporated to dryness, and column chromatography (silica gel, dichloromethane) was performed to obtain compound B-3. Mass 11.1g, yield 58%.
Toluene (69 ml), compound B-3 (7.0g, 22.0mmol), 4-biphenylboronic acid (5.23g, 26.4mmol), ethanol (34 ml), a potassium carbonate solution (2M, 34.0ml) and tetratriphenylphosphine palladium (1.27mg, 0.0011mmol) were sequentially added to a 500ml reaction flask, and refluxed for 4 hours under nitrogen protection, after the reaction was completed, the reaction solution was cooled to room temperature, washed with water, extracted with dichloromethane, combined with organic phases, dried and concentrated, and recrystallized with toluene to obtain compound C-5. Mass 6.42g, yield 67%.
Under nitrogen protection, compound C-5 (6.53g, 15.0mmol), compound D-1 (6.34g, 12.5 mmol), sodium tert-butoxide (3.60g, 37.5 mmol), toluene (190 ml), dibenzylideneacetone dipalladium (57.23mg, 0.0625 mmol), and tri-tert-butylphosphine (12.65mg, 0.0625 mmol) were sequentially added to a 500ml reaction flask, and reacted under reflux for 24 hours, and after the reaction was completed, the reaction solution was cooled to room temperature. The reaction solution was extracted with dichloromethane, the organic phases were combined, the organic phase was washed with water, dried, filtered through celite in succession, and the filtrate was concentrated and recrystallized from ethanol to give compound 215. Mass 8.30g, yield 77%. The purity of the solid is not less than 99.9% by HPLC. Mass spectrum m/z:861.4427 (theoretical value: 861.4335). Theoretical element content (%) C 66 H 55 N: c,91.95; h,6.43; n,1.62, measured elemental content (%): c,91.84; h,6.57; n,1.59. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.65 (s, 1H), 8.47 (d, 1H), 8.19 (s, 1H), 8.06-8.02 (m, 2H), 7.98 (d, 1H), 7.96-7.90 (m, 3H), 7.89-7.80 (m, 5H), 7.75 (d, 1H), 7.72-7.67 (m, 3H), 7.65 (d, 2H), 7.62-7.57 (m, 3H), 7.53-7.49 (m, 3H), 7.46-7.42 (m, 4H), 7.35-7.31 (m, 1H), 1.75 (s, 6H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Synthetic example 9: preparation of Compound 225
The 4-boronic acid-9,9-dimethylfluorene in synthesis example 8 was changed to 9,9-dimethylfluorene-1-boronic acid in equimolar amount, the 4-biphenylboronic acid was changed to phenylboronic acid in equimolar amount, and the compound D-1 was changed to the compound D-3 in equimolar amount, and the other steps were the same to obtain the compound 225. Mass 6.36g, yield 74%. The purity of the solid is not less than 99.9% by HPLC. Mass spectrum m/z:687.3014 (theoretical value: 687.2926). Theoretical element content (%) C 53 H 37 N: c,92.54; h,5.42; n,2.04, measured elemental content (%): c,92.62; h,5.36; and N,2.02. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.28 (s, 1H), 8.18 (s, 1H), 8.08-8.02 (m, 3H), 7.98 (d, 1H), 7.96-7.89 (m, 3H), 7.83 (d, 1H), 7.76-7.71 (m, 2H), 7.68-7.62 (m, 4H), 7.61-7.54 (m, 4H), 7.51-7.46 (m, 3H), 7.46-7.42 (m, 3H), 7.36-7.31 (m, 1H), 7.30-7.27 (m, 1H), 2.36 (s, 3H), 1.80 (s, 6H). The above results confirmed that the obtained product was the objective product.
Synthesis example 10: preparation of Compound 232
After replacing 9,9-dimethyl-2-bromofluorene in synthesis example 2 with equimolar 4-bromo-9,9-diphenylfluorene and equimolar 4-amino-3-chlorobenzeneboronic acid pinacol ester with 3-amino-4-chlorophenylboronic acid pinacol ester, the same procedure was repeated except for the above step, compound 232 was obtained. Mass 8.08g, yield 71%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:909.4421 (theoretical value: 909.4335). Theoretical element content (%) C 70 H 55 N: c,92.37; h,6.09; n,1.54, measured elemental content (%): c,92.51; h,6.04; and N is 1.45. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.20 (d, 1H), 7.98 (d, 1H), 7.89 (s, 1H), 7.87-7.82 (m, 2H), 7.77-7.69 (m, 6H), 7.67 (s, 1H), 7.62-7.57 (m, 2H), 7.57-7.51 (m, 2H), 7.52-7.46 (m, 4H), 7.47-7.41 (m, 2H), 7.42-7.36 (m, 1H), 7.36-7.29 (m, 3H), 7.28-7.20 (m, 6H), 7.14-7.07 (m, 5H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Synthetic example 11: preparation of Compound 240
Compound 240 was obtained by replacing phenylboronic acid in Synthesis example 1 with equimolar ((1r, 3r) -adamantan-1-yl) boronic acid and performing the same procedures. Mass 8.02g, yield 71%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z:843.4901 (theoretical value: 843.4804). Theoretical element content (%) C 64 H 61 N: c,91.06; h,7.28; n,1.66, measured elemental content (%): c,91.10; h,7.26; n,1.64. 1 H NMR(600MHz,CDCl 3 ) (delta, ppm) 8.38 (s, 1H), 8.36 (s, 1H), 8.15 (s, 1H), 8.07-8.00 (m, 4H), 7.94 (d, 1H), 7.84-7.80 (m, 2H), 7.76-7.71 (m, 2H), 7.68-7.63 (m, 4H), 7.61-7.57 (m, 1H), 7.51-7.42 (m, 4H), 7.06 (d, 1H), 2.15-2.03 (m, 9H), 1.91-1.82 (m, 4H), 1.77 (s, 6H), 1.74-1.70 (m, 2H), 1.27 (s, 18H). The above results confirmed that the obtained product was the objective product.
Device embodiments
Description of organic materials: the organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.
Description of the substrate: the ITO glass substrate was purchased from shenzhen south glass display technology ltd. The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then is ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C.
Description of vapor deposition System: the device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process -5 Below Pa, respectively evaporating an organic layer and a metal electrode by replacing the mask plateThe deposition rate was measured by an Inficon SQM160 quartz crystal film thickness measuring instrument, and the film thickness was measured by a quartz crystal oscillator.
Description of the test System: a joint IVL test system is formed by test software, a computer, a K2400 digital source meter produced by Keithley of the United states and a PR788 spectral scanning luminance meter produced by Photo Research of the United states to test the driving voltage, the luminous efficiency, the service life and the color coordinate of the organic electroluminescent device.
Example 1: preparation of organic electroluminescent device 1
ITO is used as an anode on a glass substrate; the compound 1 of the invention is vacuum evaporated on the anode to be used as a hole transport layer, and the evaporation thickness is 30nm; vacuum evaporation of CBP Ir (ppy) on hole transport layer 3 (95); performing vacuum evaporation on the luminescent layer to form Bphen as a hole blocking layer, wherein the evaporation thickness is 10nm; performing vacuum evaporation on the hole barrier layer to form Bphen as an electron transport layer, wherein the evaporation thickness is 30nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1nm; al is vacuum-evaporated on the electron injection layer to form a cathode, and the thickness of the vapor-deposited layer is 100nm.
The structure of the device is as follows: ITO/Compound 1,30nm/CBP Ir (ppy) 3 (95:5),30nm/Bphen,10nm/Bphen,30nm/LiF,1nm/Al,100nm
Examples 2 to 31: preparation of organic electroluminescent devices 2 to 31
By replacing compound 1 in the hole transport layer in example 1 with compound 1, compound 2, compound 6, compound 12, compound 19, compound 26, compound 31, compound 36, compound 39, compound 40, compound 46, compound 51, compound 53, compound 61, compound 65, compound 73, compound 80, compound 94, compound 98, compound 111, compound 120, compound 123, compound 136, compound 148, compound 151, compound 184, compound 194, compound 215, compound 225, compound 232, and compound 240, respectively, the same procedure was repeated, thereby obtaining organic electroluminescent devices 2 to 31.
Comparative examples 1 to 2: preparation of comparative organic electroluminescent devices 1 to 2
The compound 1 in the hole transport layer of example 1 was replaced with NPB and R-1, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 2.
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 31 of the present invention and comparative examples 1 to 2 are shown in table 1.
Table 1 test data of light emitting characteristics of organic electroluminescent device
As can be seen from table 1, the organic electroluminescent device of the present invention has higher driving voltage, higher luminous efficiency, and longer life than those of the comparative organic electroluminescent devices 1 to 2. Compared with NPB or R-1, the spirobifluorene-containing derivative of the formula I has a more proper HOMO energy level, namely the HOMO energy level is more matched with that of the anode and the light-emitting layer, the hole injection barrier is lower, holes can be effectively injected into the light-emitting layer to realize effective recombination of the holes and electrons, and therefore, a device with the hole transport layer containing the derivative of the formula I has lower driving voltage and higher light-emitting efficiency. In addition, the spirobifluorene-containing derivative of the formula I has better stability, so that the service life of a device containing the derivative is longer. In particular, compounds containing alkyl groups such as tert-butyl, isopropyl, ethyl, methyl, adamantyl and the like or deuterium in the structure have higher stability than compounds containing no alkyl group and deuterium, and the service life of the device is relatively longer.
Claims (5)
1. A derivative containing spirobifluorene is characterized by having a structural general formula shown as I-1 to I-6,
wherein, R is 0 One selected from methyl and phenyl;
m is selected from an integer from 0 to 4, n is selected from an integer from 0 to 3, k is selected from an integer from 0 to 2, R is selected from one of hydrogen, deuterium, methyl, isopropyl and tert-butyl, each R is the same or different, R 'is selected from one of hydrogen and deuterium, and each R' is the same or different; when R is selected from methyl, isopropyl or tert-butyl, (R) m M in (1) is selected from 0 or 1;
the L is selected from a single bond or one of the groups shown as the following,
said L 1 Selected from a single bond or phenylene;
ar is 0 Is selected from one of the groups shown below,
p is selected from an integer of 0 to 5, q is selected from an integer of 0 to 7, m is selected from an integer of 0 to 4, R 1 One selected from hydrogen and deuterium, each R 1 The same or different; the R is 1 ' one selected from hydrogen, deuterium, methyl, isopropyl, tert-butyl, each R 1 ' same or different, when R 1 When the group is selected from methyl, isopropyl and tert-butyl, (R) 1 ') p P in (1) is selected from 1.
2. A spirobifluorene-containing derivative according to claim 1,ar is 0 Selected from one of the following groups,
3. a spirobifluorene-containing derivative is characterized in that the spirobifluorene-containing derivative of the formula I is selected from one of the structures shown in the specification,
4. an organic electroluminescent element comprising an anode, an organic layer containing the spirobifluorene-containing derivative according to any one of claims 1 to 3, and a cathode in this order.
5. An organic electroluminescent device according to claim 4, wherein the organic layer comprises a hole transport layer containing the spirobifluorene-containing derivative according to any one of claims 1 to 3.
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