Organic phosphorus luminescent compound, preparation method thereof and organic electroluminescent device
阅读说明：本技术 一种有机磷光发光化合物及其制备方法和有机电致发光器件 (Organic phosphorus luminescent compound, preparation method thereof and organic electroluminescent device ) 是由 王辉 高旭 王猛 李小龙 刘志远 李建行 马晓宇 于 2019-11-11 设计创作，主要内容包括：本发明涉及一种有机磷光发光化合物及其制备方法和有机电致发光器件,属于有机光电材料技术领域。本发明的有机磷光发光化合物具有式G所示结构：<Image he="507" wi="700" file="DDA0002267258980000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明提供的新型结构的有机磷光发光化合物,通过选择特定的桥联配体结合,调节化合物的波长,得到的有机磷光金属化合物在用于有机电致发光器件后,使得器件的发光效率有显著提高,而且寿命长。本发明提供有机磷光发光化合物的制备方法,具有合成工艺简单,产物纯度高的优点。(The invention relates to an organic phosphorus luminescent compound, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of organic photoelectric materials. The organic phosphorescent light-emitting compound has a structure shown in a formula G: the organic phosphorescent metal compound with the novel structure provided by the invention is combined by selecting a specific bridging ligand, the wavelength of the compound is adjusted, and the obtained organic phosphorescent metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is obviously improved, and the service life of the device is long. The present invention provides organic phosphorusThe preparation method of the light photochemical compound has the advantages of simple synthesis process and high product purity.)
1. An organic phosphorus luminescent compound having a structure represented by formula G:
wherein: r1、R2、R4Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused ring group, or substituted or unsubstituted spiro ring;
R3selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aromatic heterocyclic group;
R1、R2、R3the substitution position is any position of the ring; r1The number of substituents is 0 to 4, R2The number of the substituents is 0-2, R3The number of the substituents is 0 to 3.
2. The organophosphorus photoluminescent compound of claim 1, wherein R is1、R2、R4Each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C16 condensed ring group, or substituted or unsubstituted C5-C15 spiro ring.
3. The organophosphorus photoluminescent compound of claim 1, wherein R is3Is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, or substituted or unsubstituted C4-C12 aromatic heterocyclic group.
4. The organophosphorus photoluminescent compound of claim 1, wherein R is1And R2Independently form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C12 aromatic heterocycle, a substituted or unsubstituted C10-C18 condensed ring or a substituted or unsubstituted C5-C15 spiro ring with other substituents on the ring.
5. The organophosphorus photoluminescent compound of claim 1, wherein R is3And other substituents on the ring mutually form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring or a substituted or unsubstituted C4-C12 aromatic heterocyclic ring.
6. The organic phosphorus-light emitting compound according to claim 1, selected from any one of the following structures:
7. a method for preparing an organic phosphorescent light-emitting compound according to any one of claims 1 to 6, comprising the steps of:
step 1, adding a raw material A and iridium trichloride into a mixed solvent of ethylene glycol ethyl ether/water, and fully reacting to obtain a bridging ligand intermediate B;
step 2, adding potassium carbonate and ethylene glycol ethyl ether into the intermediate B and the diketone derivative, and fully reacting to obtain an organic phosphorus light luminescent compound G;
the synthetic route is as follows:
8. the method for preparing an organic phosphorescent compound according to claim 7, wherein the reaction condition in the step 1 is reflux for 24 hours under nitrogen protection, and the reaction condition in the step 2 is reflux for 24 hours under nitrogen protection by heating at 120 ℃.
9. An organic electroluminescent device comprising the organic phosphorescent light-emitting compound according to any one of claims 1 to 6.
10. The organic electroluminescent device according to claim 9, comprising: a first electrode, a second electrode and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains the organic phosphorus luminescent compound according to any one of claims 1 to 6; the organic phosphorescent light-emitting compound is in a single form or in two forms of a polymorphous form.
Technical Field
The invention relates to an organic phosphorus luminescent compound, a preparation method thereof and an organic electroluminescent device, in particular to a red phosphor used as a dopant of a luminescent layer of the organic electroluminescent device.
Background
In recent years, as the size of display devices is getting larger, flat display devices occupying less space are more and more required. The flat panel display device includes an organic electroluminescent device, also called an Organic Light Emitting Diode (OLED). The technology of the organic electroluminescent device is developing at a great speed, and many prototypes have been disclosed.
Since the invention of organic Electroluminescent (EL) materials, the organic Electroluminescent (EL) materials have higher luminous efficiency (up to ten thousand cd/m) due to self-luminous property2) Light weight, high response speed, wide visual angle range (up to 160 deg.), low driving voltage<10V) and wide working temperature range (working under the condition of minus 45-80 ℃), rigid display can be formed, flexible display can be realized, large-screen display is easy to realize, and the like, which is called as a 'fantasy display' by the people in the industry, so that the organic EL is gradually developed into the most advantageous technology in the field of new-generation flat panel display.
But their development is limited by factors such as their efficiency and lifetime. In organic EL materials, it is a great challenge to effectively improve the luminous efficiency and the long lifetime, and therefore, it is required to select a novel organic material to develop a novel luminous layer meeting the practical requirement.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides an organic phosphorus luminescent compound, a preparation method thereof and an organic electroluminescent device. The organic electroluminescent device prepared from the organic phosphorus luminescent compound has high luminous efficiency and long service life.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides an organic phosphorus luminescent compound, which has a structure shown in a formula G:
wherein: r1、R2、R4Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted fused ring group, or substituted or unsubstituted spiro ring;
R3selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aromatic heterocyclic group;
R1、R2、R3the substitution position is any position of the ring; r1The number of substituents is 0 to 4, R2The number of the substituents is 0-2, R3The number of the substituents is 0 to 3.
In the above technical solutions, R is preferable1、R2、R4Each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C16 condensed ring group, or substituted or unsubstituted C5-C15 spiro ring.
In the above technical solutions, R is preferable3Is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, or substituted or unsubstituted C4-C12 aromatic heterocyclic group.
In the above technical solutions, R is preferable1And R2Independently form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C12 aromatic heterocycle, a substituted or unsubstituted C10-C18 condensed ring or a substituted or unsubstituted C5-C15 spiroAnd (4) a ring.
In the above technical solutions, R is preferable3And other substituents on the ring mutually form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring or a substituted or unsubstituted C4-C12 aromatic heterocyclic ring.
The alkyl is a straight-chain alkyl, a branched-chain alkyl, a cyclic alkyl, a straight-chain alkyl substituted by at least one substituent, a branched-chain alkyl substituted by at least one substituent or a cyclic alkyl substituted by at least one substituent; wherein, the substituent is one or more of halogen, deuterium, methyl, ethyl, cyano, isopropyl and hydroxyl.
The aryl group in the present invention is an unsubstituted aryl group or an aryl group substituted with at least one substituent; wherein the substituents are independently selected from the group consisting of halogen, deuterium, cyano, methyl, ethyl, isopropyl, and combinations thereof.
The hetero atom in the aromatic heterocyclic group in the present invention is nitrogen, sulfur or oxygen; the substituents are independently selected from the group consisting of halogen, deuterium, methyl, isopropyl, cyano, hydroxy or mercapto and combinations thereof.
The substituent on the substituent group in the invention is at least one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C18 condensed ring group and substituted or unsubstituted C5-C15 spiro ring.
In the above technical solution, it is most preferable that the organic phosphorescent light emitting compound is selected from any one of the following structures:
some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of the groups and the substituted groups and substituted positions thereof, which is not described in detail herein.
The invention also provides a preparation method of the organic phosphorescent light-emitting compound, which comprises the following steps:
step 1, adding a raw material A and iridium trichloride into a mixed solvent of ethylene glycol ethyl ether/water, and fully reacting to obtain a bridging ligand intermediate B;
step 2, adding potassium carbonate and ethylene glycol ethyl ether into the intermediate B and the diketone derivative, and fully reacting to obtain an organic phosphorus light luminescent compound G;
the synthetic route is as follows:
wherein R is1、R2、R3、R4And the number of the substituents are the same as those defined in formula G, and are not described herein.
In the technical scheme, the reaction condition of the step 1 is reflux for 24 hours under the protection of nitrogen, and the reaction condition of the step 2 is reflux for 24 hours under the protection of nitrogen by heating at 120 ℃.
The present invention also provides an organic electroluminescent device comprising the organic phosphorescent light-emitting compound represented by chemical formula G of the present invention.
The organic electroluminescent device includes:
a first electrode (cathode), a second electrode (anode) and an organic layer arranged between the two electrodes, wherein the organic layer contains the organic phosphorescent compound shown in the chemical formula G of the invention; the organic phosphorus luminescent compound of formula G of the present invention may be in a single form or in two forms of polymorphous form.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
The organic electroluminescent device comprises at least one functional layer containing the organic phosphorescent light-emitting compound represented by the formula G of the present invention.
The organic electroluminescent device includes a light emitting layer containing the organic phosphorescent light emitting compound represented by the chemical formula G of the present invention.
The luminescent layer of the organic electroluminescent device comprises a main material and a phosphorescent material, wherein the phosphorescent material is an organic phosphorescent luminescent compound shown in a chemical formula G. The mixing ratio of the host material of the light-emitting layer and the phosphorescent material is preferably 90: 10-99.5: 0.5.
the device of the present invention can be used for organic light emitting devices, organic solar cells, electronic paper, organic photoreceptors, organic light emitting diodes, and the like.
The invention has the beneficial effects that:
the organic phosphorescent metal compound with the novel structure provided by the invention is combined by selecting a specific bridging ligand, the wavelength of the compound is adjusted, and the obtained organic phosphorescent metal compound is used for an organic electroluminescent device, so that the luminous efficiency of the device is obviously improved, and the service life of the device is long.
The preparation method of the organic phosphorescent light-emitting compound provided by the invention has the advantages of simple synthesis process and high product purity.
Detailed Description
In order to further illustrate the present invention, the following will describe the organic phosphorescent compound, the preparation method thereof and the organic electroluminescent device in detail with reference to the examples.
The following compounds G-001, G-006, G-031, G-091, G-094 and G-096 are exemplified in the present invention, and the preparation methods of the remaining compounds are similar and will not be further exemplified herein.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种有机金属铱配合物和其制备方法及电致发光器件