Luminescent auxiliary material containing triarylamine functional groups, preparation method thereof and organic electroluminescent device
1. A luminescent auxiliary material, characterized in that the luminescent auxiliary material has a structure of formula (I),
wherein X is selected fromSingle bond, O, S, SiR3R4、CR5R6、NR7；
The R is3、R4、R5、R6、R7Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C3-C15 heterocycloalkyl;
the R is3、R4、R5、R6Or R7May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
the R is1、R2Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic group, phosphoric group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R is1Or R2May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
a or b is respectively selected from an integer of 0-4;
ar is1、Ar2Each independently selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C20 heteroaryl, and substituted or unsubstituted C10-C30 condensed ring group;
said L1、L2Or L3Each independently selected from a single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C5-C30, substituted or unsubstituted cycloalkyl of C3-C30, and substituted or unsubstituted heterocycloalkyl of C3-C30.
2. A luminescent support material as claimed in claim 1, wherein R is a group of atoms1、R2Each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of C1-C10, substituted or unsubstituted cycloalkyl of C3-C15, substituted or unsubstituted heterocycloalkyl of C3-C15, substituted or unsubstituted aryl of C6-C25, and substituted or unsubstituted heteroaryl of C3-C25;
the R is1、R2Wherein, the heteroatom in the heterocycloalkyl of C3-C20 comprises one or more of N, O, S, Si, P and Se;
the R is1、R2The heteroatom in the heteroaryl of C3-C30 comprises one or more of N, O, S, Si, P and Se.
3. The light-emitting auxiliary material according to claim 1, wherein the single-ring or multi-ring structure comprises an alicyclic ring and/or an aromatic ring;
one or more carbon atoms in the cycloaliphatic ring may be replaced by a heteroatom;
one or more carbon atoms in the aromatic ring may be replaced with a heteroatom;
the heteroatoms include one or more of nitrogen, oxygen, and sulfur.
4. The luminescent auxiliary material according to claim 1, wherein Ar is1、Ar2Each independently selected from substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C18 heteroaryl, and substituted or unsubstituted C10-C25 condensed ring group;
ar is1、Ar2Wherein, the heteroatom in the heterocycloalkyl of C3-C30 comprises one or more of N, O, S, Si, P and Se;
ar is1、Ar2The heteroatom in the heteroaryl of C3-C20 comprises one or more of N, O, S, Si, P and Se.
5. A luminescent support material as claimed in claim 1, wherein L is1、L2Or L3Each independently selected from single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C5-C25;
said L1、L2Or L3Wherein the hetero atom in the C5-C30 heteroarylene group comprises one or more of N, O, S, Si, P and Se;
said L1、L2Or L3The heteroatom in the C3-C30 heterocycloalkyl comprises one or more of N, O, S, Si, P and Se.
6. The light-emitting auxiliary material according to claim 1, wherein the light-emitting auxiliary material is an organic electroluminescent auxiliary material containing a triarylamine functional group;
the organic electroluminescent auxiliary material is used for forming an organic light-emitting auxiliary layer.
7. The luminescent auxiliary material according to claim 1, wherein the luminescent auxiliary material is represented by any one of formulas 1 to 84:
8. a method for preparing a luminescent auxiliary material according to any one of claims 1 to 7, comprising the steps of:
1) under a protective atmosphere, mixing a raw material compound with a structure shown in a formula A, a raw material compound with a structure shown in a formula B and an organic solvent, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and reacting to obtain an intermediate 1;
2) mixing the intermediate 1 obtained in the step, the raw material compound with the structure of the formula C and the organic solvent under a protective atmosphere, adding the palladium catalyst, the phosphine ligand and the sodium tert-butoxide again, and continuing to react to obtain an intermediate 2;
3) under a protective atmosphere, mixing the intermediate 2 obtained in the step, the raw material compound with the structure of the formula D and an organic-inorganic mixed solvent, adding palladium tetratriphenylphosphine and potassium carbonate, and reacting again to obtain an intermediate 3;
4) mixing the intermediate 3 obtained in the step, the raw material compound with the structure shown in the formula E and an organic-inorganic mixed solvent in a protective atmosphere, adding palladium tetratriphenylphosphine and potassium carbonate again, and finally reacting to obtain the light-emitting auxiliary material with the structure shown in the formula (I);
wherein Hal1～Hal4Are respectively selected from halogen.
9. An organic electroluminescent device, comprising a light-emitting auxiliary material; the luminescent auxiliary material comprises the luminescent auxiliary material as defined in any one of claims 1 to 7 or the luminescent auxiliary material prepared according to claim 8.
10. The organic electroluminescent device according to claim 9, wherein the light-emission assisting material is located in the light-emission assisting layer;
the light-emitting auxiliary layer is positioned between the hole transport layer and the light-emitting layer.
Background
Organic light emitting devices are gradually entering the human field of vision as a new and promising display technology. An OLED is an electroluminescent device formed of a multi-layered organic thin film structure in which an organic thin film is a film of an organic light emitting material formed on a substrate using an evaporation, deposition, or spin coating process.
Many improvements have been made in the existing research to make the organic EL device practical. For example, it is known that high efficiency and high durability can be achieved by further distributing various functions of a laminated structure and forming an anode, and a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode, and the like are provided on a substrate.
With this organic EL device, charges injected from the two electrodes are recombined in the light emitting layer to obtain light emission. In this case, how to efficiently transfer charges of holes and electrons to the light emitting layer is important, and the device is required to have excellent carrier balance. Also, the light emitting efficiency is improved by enhancing a hole injecting property and an electron blocking property of blocking electrons injected from the cathode to increase a recombination probability of holes and electrons, and by confining excitons generated in the light emitting layer. Therefore, the role of the hole transport material is so important that a hole transport material having high hole injection property, high hole mobility, high electron blocking property and high electron durability is required.
The research on organic electroluminescent materials has been widely carried out in academia and industry, but the development of stable and efficient organic layer materials for organic electronic devices has not been fully developed so far, and the industrialization of the technology still faces many key problems, so that the development of new materials is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a novel light-emitting auxiliary material, a method for preparing the same, and an organic electroluminescent device, wherein the light-emitting auxiliary material is helpful for producing an organic electroluminescent device with low driving voltage, high light-emitting efficiency, and/or long service life characteristics.
The invention provides a luminous auxiliary material, which is characterized in that the luminous auxiliary material has a structure shown in a formula (I),
wherein X is selected from single bond O, S, SiR3R4、CR5R6、NR7；
The R is3、R4、R5、R6、R7Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C3-C15 heterocycloalkyl;
the R is3、R4、R5、R6Or R7May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
the R is1、R2Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic group, phosphoric group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R is1Or R2May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
a or b is respectively selected from an integer of 0-4;
ar is1、Ar2Each independently selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, and substituted or unsubstituted C6-C30 arylA substituted or unsubstituted heteroaryl of C3-C20, a substituted or unsubstituted condensed ring group of C10-C30;
said L1、L2Or L3Each independently selected from a single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C5-C30, substituted or unsubstituted cycloalkyl of C3-C30, and substituted or unsubstituted heterocycloalkyl of C3-C30.
Preferably, said R is1、R2Each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of C1-C10, substituted or unsubstituted cycloalkyl of C3-C15, substituted or unsubstituted heterocycloalkyl of C3-C15, substituted or unsubstituted aryl of C6-C25, and substituted or unsubstituted heteroaryl of C3-C25;
the R is1、R2Wherein, the heteroatom in the heterocycloalkyl of C3-C20 comprises one or more of N, O, S, Si, P and Se;
the R is1、R2The heteroatom in the heteroaryl of C3-C30 comprises one or more of N, O, S, Si, P and Se.
Preferably, the monocyclic or polycyclic structure includes alicyclic rings and/or aromatic rings;
one or more carbon atoms in the cycloaliphatic ring may be replaced by a heteroatom;
one or more carbon atoms in the aromatic ring may be replaced with a heteroatom;
the heteroatoms include one or more of nitrogen, oxygen, and sulfur.
Preferably, Ar is1、Ar2Each independently selected from substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C18 heteroaryl, and substituted or unsubstituted C10-C25 condensed ring group;
ar is1、Ar2Wherein, the heteroatom in the heterocycloalkyl of C3-C30 comprises one or more of N, O, S, Si, P and Se;
ar is1、Ar2The heteroatom in the heteroaryl of C3-C20 comprises one or more of N, O, S, Si, P and Se.
Preferably, said L1、L2Or L3Each independently selected from single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C5-C25;
said L1、L2Or L3Wherein the hetero atom in the C5-C30 heteroarylene group comprises one or more of N, O, S, Si, P and Se;
said L1、L2Or L3The heteroatom in the C3-C30 heterocycloalkyl comprises one or more of N, O, S, Si, P and Se.
Preferably, the luminescent auxiliary material is an organic electroluminescent auxiliary material containing triarylamine functional groups;
the organic electroluminescent auxiliary material is used for forming an organic light-emitting auxiliary layer.
Preferably, the luminescence auxiliary material is represented by any one of formula 1 to formula 84:
the invention provides a preparation method of the luminous auxiliary material, which comprises the following steps:
1) under a protective atmosphere, mixing a raw material compound with a structure shown in a formula A, a raw material compound with a structure shown in a formula B and an organic solvent, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and reacting to obtain an intermediate 1;
2) mixing the intermediate 1 obtained in the step, the raw material compound with the structure of the formula C and the organic solvent under a protective atmosphere, adding the palladium catalyst, the phosphine ligand and the sodium tert-butoxide again, and continuing to react to obtain an intermediate 2;
3) under a protective atmosphere, mixing the intermediate 2 obtained in the step, the raw material compound with the structure of the formula D and an organic-inorganic mixed solvent, adding palladium tetratriphenylphosphine and potassium carbonate, and reacting again to obtain an intermediate 3;
4) mixing the intermediate 3 obtained in the step, the raw material compound with the structure shown in the formula E and an organic-inorganic mixed solvent in a protective atmosphere, adding palladium tetratriphenylphosphine and potassium carbonate again, and finally reacting to obtain the light-emitting auxiliary material with the structure shown in the formula (I);
Ar2-B(OH)2
E；
wherein Hal1～Hal4Are respectively selected from halogen.
The invention also provides an organic electroluminescent device, which comprises a luminescent auxiliary material; the luminescent auxiliary material comprises the luminescent auxiliary material according to any one of the above technical schemes or the luminescent auxiliary material prepared according to the above technical schemes.
Preferably, the luminescence auxiliary material is located in the luminescence auxiliary layer;
the light-emitting auxiliary layer is positioned between the hole transport layer and the light-emitting layer.
The invention provides a luminous auxiliary material which has a structure shown in a formula (I). Compared with the prior art, the luminescent auxiliary material provided by the invention is an organic electroluminescent auxiliary material containing triarylamine functional groups, the hole transmission efficiency and the electron blocking capability are improved to a great extent, and the charge balance of holes and electrons in a luminescent layer is increased, so that luminescence is well formed in the luminescent layer instead of the surface of the hole transmission layer, and the maximization efficiency and the service life are judged. The introduction of structures such as benzo five-membered (hetero) rings, six-membered heterocycles and the like reduces the symmetry of molecules, increases conformational isomers of the molecules, has a rigid planar structure, is not easy to crystallize and aggregate among the molecules, and improves the yield of the manufactured organic EL elements. Therefore, the organic luminescent compound of the present invention can improve the characteristics of luminous efficiency, driving voltage, service life, etc. in an organic luminescent device.
The light-emitting auxiliary material provided by the invention can be used for producing an organic electroluminescent device with low driving voltage, high luminous efficiency and/or long service life.
The experimental result shows that compared with the existing organic electroluminescent device, the organic electroluminescent device prepared by using the luminescent auxiliary material provided by the invention has the advantages that the driving voltage is obviously reduced, and the luminous efficiency and the service life are obviously improved.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and analytical purification is preferably employed in the present invention.
In the present invention, a person skilled in the art can correctly understand that the meanings represented by the two expressions (×) and (×) are equivalent, and the presence or absence of parentheses does not affect the actual meanings thereof.
The invention provides a luminous auxiliary material, which has a structure shown in a formula (I),
wherein X is selected from single bond O, S, SiR3R4、CR5R6、NR7；
The R is3、R4、R5、R6、R7Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C3-C15 heterocycloalkyl;
the R is3、R4、R5、R6Or R7May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
the R is1、R2Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic group, phosphoric group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R is1Or R2May be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure;
a or b is respectively selected from an integer of 0-4;
ar is1、Ar2Each independently selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C20 heteroaryl, and substituted or unsubstituted C10-C30 condensed ring group;
said L1、L2Or L3Each independently selected from a single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C5-C30, substituted or unsubstituted cycloalkyl of C3-C30, and substituted or unsubstituted heterocycloalkyl of C3-C30.
In the present invention, X is selected from the group consisting of a single bond, O, S, SiR3R4、CR5R6、NR7. The single bond is a connecting bond, and means that elements at two ends of the X substituent can be directly bonded.
In the present invention, said R3、R4、R5、R6、R7Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C3-C15 heterocycloalkyl, more preferably substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C25 heteroaryl, substituted or unsubstituted C3-C15 cycloalkyl and substituted or unsubstituted C3-C10 heterocycloalkyl.
In the present invention, the alkyl group having 1 to 30 may be an alkyl group having 2 to 25 carbon atoms, an alkyl group having 3 to 20 carbon atoms, or an alkyl group having 5 to 15 carbon atoms. The aryl of C6-C30 can be C7-C25 aryl, or C8-C20 aryl, or C10-C15 aryl. The heteroaryl of C3-C30 can be a heteroaryl of C4-C25, a heteroaryl of C5-C20 or a heteroaryl of C8-C15. Wherein the heteroatoms in the heteroaryl group preferably comprise one or more of N, O, S, Si, P and Se. The cycloalkyl of C3-C20 can be C4-C18, C5-C15 or C6-C13. The heterocycloalkyl of C3-C15 can be a heterocycloalkyl of C4-C13 or a heterocycloalkyl of C5-C10. Wherein the heteroatoms in the heterocycloalkyl group preferably include one or more of N, O, S, Si, P and Se.
In the present invention, said R3、R4、R5、R6Or R7And may be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure. Among them, the monocyclic or polycyclic structure preferably includes an alicyclic ring and/or an aromatic ring, more preferably an alicyclic ring or an aromatic ring of C1 to C30. In particular, one or more carbon atoms in the cycloaliphatic ring may preferably be replaced by heteroatoms. Preferably, one or more carbon atoms in the aromatic ring may be replaced by a heteroatom. In particular, the heteroatoms preferably include one or more of nitrogen, oxygen and sulfur.
In the present invention, said R1、R2Each independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, more preferably hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 heterocycloalkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C3-C25 heteroaryl.
In the present invention, the alkyl group having 1 to 25 may be an alkyl group having 2 to 20 carbon atoms, an alkyl group having 3 to 15 carbon atoms, or an alkyl group having 5 to 10 carbon atoms. The cycloalkyl of C3-C20 can be C4-C18, C5-C15 or C6-C13. The heterocycloalkyl of C3-C20 can be the heterocycloalkyl of C4-C18, the heterocycloalkyl of C5-C15 or the heterocycloalkyl of C6-C13. Wherein the heteroatoms in the heterocycloalkyl group preferably include one or more of N, O, S, Si, P and Se. The alkenyl of C2-C30 can be alkenyl of C3-C25, or alkenyl of C5-C20, or alkenyl of C8-C15. The alkynyl of C2-C30 can be the alkynyl of C3-C25, or the alkynyl of C5-C20, or the alkynyl of C8-C15. The aryl of C6-C30 can be C7-C25 aryl, or C8-C20 aryl, or C10-C15 aryl. The heteroaryl of C3-C30 can be a heteroaryl of C4-C25, a heteroaryl of C5-C20 or a heteroaryl of C8-C15. Wherein the heteroatoms in the heteroaryl group preferably comprise one or more of N, O, S, Si, P and Se.
In the present invention, said R1Or R2And may be linked to one or more adjacent substituents to form a monocyclic or polycyclic structure. Among them, the monocyclic or polycyclic structure preferably includes an alicyclic ring and/or an aromatic ring. In particular, one or more carbon atoms in the cycloaliphatic ring may preferably be replaced by heteroatoms. Preferably, one or more carbon atoms in the aromatic ring may be replaced by a heteroatom. In particular, the heteroatoms preferably include one or more of nitrogen, oxygen and sulfur.
In the invention, a is an integer of 0 to 4, and specifically may be 0, 1,2, 3 or 4. B is an integer of 0 to 4, and specifically may be 0, 1,2, 3 or 4.
In the present invention, Ar1、Ar2Each independently selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C20 heteroaryl, and substituted or unsubstituted C10-C30 fused ring group, more preferably substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C18 heteroaryl, and substituted or unsubstituted C10-C25 fused ring group.
In the invention, the cycloalkyl of C3-C30 can be C4-C25, C5-C20 or C8-C15. The heterocycloalkyl of C3-C30 can be the heterocycloalkyl of C4-C25, the heterocycloalkyl of C5-C20 or the heterocycloalkyl of C8-C15. Wherein the heteroatoms in the heterocycloalkyl group preferably include one or more of N, O, S, Si, P and Se. The aryl of C6-C30 can be C7-C25 aryl, or C8-C20 aryl, or C10-C15 aryl. The heteroaryl of C3-C20 can be a heteroaryl of C4-C18, a heteroaryl of C5-C15 or a heteroaryl of C6-C12. Wherein the heteroatoms in the heteroaryl group preferably comprise one or more of N, O, S, Si, P and Se. The C10-C30 condensed ring group can be C11-C28 condensed ring group, or C12-C25 condensed ring group, or C13-C20 condensed ring group.
In the present invention, L1、L2Or L3Each independently selected from a single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstituted heteroarylene of C5-C30, substituted or unsubstituted cycloalkyl of C3-C30, and substituted or unsubstituted heterocycloalkyl of C3-C30, more preferably a single bond, substituted or unsubstituted arylene of C6-C25, and substituted or unsubstituted heteroarylene of C5-C25.
The present invention refers to a single bond, i.e., a connecting bond, and refers to L1、L2Or L3The elements at both ends of the substituent may be directly bonded.
In the invention, the arylene of C6-C30 can be C7-C25 arylene, C8-C20 arylene, or C10-C15 arylene. The C5-C30 heteroarylene group can be a C6-C25 heteroarylene group, a C7-C20 heteroarylene group or a C6-C15 heteroarylene group. Wherein the heteroatoms in the heteroarylene group preferably comprise one or more of N, O, S, Si, P and Se. The cycloalkyl of C3-C30 can be C4-C25, C5-C20 or C8-C15. The heterocycloalkyl of C3-C30 can be the heterocycloalkyl of C4-C25, the heterocycloalkyl of C5-C20 or the heterocycloalkyl of C8-C15. Wherein the heteroatoms in the heterocycloalkyl group preferably include one or more of N, O, S, Si, P and Se.
It is to be noted that, in the present invention, the term "substituted or unsubstituted" means being substituted with one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; a substituted or unsubstituted heterocyclylamino group; a substituted or unsubstituted arylamine group; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are bonded, or no substituent.
For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
Specifically, the luminescent auxiliary material of the present invention may be represented by any one of formulas 1 to 84:
the invention also provides a preparation method of the luminescent auxiliary material, which comprises the following steps:
1) under a protective atmosphere, mixing a raw material compound with a structure shown in a formula A, a raw material compound with a structure shown in a formula B and an organic solvent, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and reacting to obtain an intermediate 1;
2) mixing the intermediate 1 obtained in the step, the raw material compound with the structure of the formula C and the organic solvent under a protective atmosphere, adding the palladium catalyst, the phosphine ligand and the sodium tert-butoxide again, and continuing to react to obtain an intermediate 2;
3) under a protective atmosphere, mixing the intermediate 2 obtained in the step, the raw material compound with the structure of the formula D and an organic-inorganic mixed solvent, adding palladium tetratriphenylphosphine and potassium carbonate, and reacting again to obtain an intermediate 3;
4) mixing the intermediate 3 obtained in the step, the raw material compound with the structure shown in the formula E and an organic-inorganic mixed solvent in a protective atmosphere, adding palladium tetratriphenylphosphine and potassium carbonate again, and finally reacting to obtain the light-emitting auxiliary material with the structure shown in the formula (I);
wherein Hal1～Hal4Are respectively selected from halogen. Specifically, fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and the like can be mentioned.
The invention is a complete and detailed integral preparation scheme, better ensures the structure and performance of the luminous auxiliary material, and the preparation method preferably comprises the following steps:
step 1, preparation of intermediate 1
Under the protection of nitrogen, dissolving a raw material A (a raw material compound with a structure of a formula A) and a raw material B (a raw material compound with a structure of a formula B) in a toluene solution, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, uniformly stirring, heating and refluxing to prepare an intermediate 1;
step 2, preparation of intermediate 2
Under the protection of nitrogen, dissolving the intermediate 1 and a raw material C (a raw material compound with a structure of a formula C) in a toluene solution, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, uniformly stirring, heating and refluxing to prepare an intermediate 2;
step 3, preparation of intermediate 3
Under the protection of nitrogen, dissolving the intermediate 2 and a raw material D (a raw material compound with a structure of a formula D) in a mixed solution of toluol and water, adding palladium tetratriphenylphosphine and potassium carbonate, uniformly stirring, heating and refluxing to prepare an intermediate 3;
step 4, preparation of chemical formula I
Under the protection of nitrogen, dissolving the intermediate 3 and the raw material E (the raw material compound with the structure of the formula E) in a mixed solution of toluene, ethanol and water, adding palladium tetratriphenylphosphine and potassium carbonate, uniformly stirring, heating and refluxing to prepare the luminescent auxiliary material with the structure of the formula (I).
The above reaction preparation process of the present invention can be seen in the following reaction formula,
more specifically, the preparation method may comprise the following steps:
the step 1) specifically comprises the following steps:
under the protection of nitrogen, dissolving a raw material A (1.0eq) and a raw material B (1.0eq) in a toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.01eq), tri-tert-butylphosphine (0.05eq) and sodium tert-butoxide (2.0eq), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 1;
the step 2) specifically comprises the following steps:
under the protection of nitrogen, dissolving the intermediate 1(1.0eq) and the raw material C (1.0eq) in a toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.01eq), tri-tert-butylphosphine (0.05eq) and sodium tert-butoxide (2.0eq), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Dissolving the solid obtained by drying in a methanol solution, heating and stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying to prepare an intermediate 2;
the step 3) specifically comprises the following steps:
under the protection of nitrogen, the intermediate 2(1.0eq) and the raw material D (1.0eq) were dissolved in toluol and water (V)tolAdding tetratriphenylphosphine palladium (0.01eq) and potassium carbonate (2.0eq) into a mixed solution of V, V and V which are 3:1:1), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, slightly cooling after the reaction is finished, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times, keeping an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, carrying out suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 3;
the step 4) specifically comprises the following steps:
under the protection of nitrogen, the intermediate 3(1.0eq) and the raw material E (1.0eq) were dissolved in toluol and water (V)tolAdding tris (dibenzylideneacetone) dipalladium (0.01eq), tri-tert-butylphosphine (0.05eq) and sodium tert-butoxide (2.0eq) into a mixed solution of V, V and V being 3:1:1), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 10:4) to obtain formula I.
The invention also provides an organic electroluminescent device, which comprises a luminescent auxiliary material; the luminescent auxiliary material comprises the luminescent auxiliary material according to any one of the above technical schemes or the luminescent auxiliary material prepared according to the above technical schemes.
In the present invention, the luminescence auxiliary material is preferably located in the luminescence auxiliary layer. More preferably, the light emission assisting layer is located between the hole transporting layer and the light emitting layer.
In the present invention, the organic electroluminescent device preferably includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode.
The organic material layer of the organic light emitting device of the present disclosure may be formed in a single layer structure, but may also be formed in a multi-layer structure in which a layer and two or more organic material layers are present. For example, the organic light emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.
As the anode material, a material having a large work function is generally preferred so that holes are smoothly injected into the organic material layer. Specific examples of anode materials that can be used in the present disclosure include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ZnO: Al or SnO2: Sb; conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDOT), polypyrrole and polyaniline, but are not limited thereto.
The hole injecting material is a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanenitrile-based hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-and polythiophene-based conductive polymer, and the like, but are not limited thereto, and may further include another compound capable of p-doping.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.
The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in a visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxyquinoline aluminum complex (Alq 3); a carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzocarbazole-, benzothiazole-, and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.
The host material of the light-emitting layer includes a condensed aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocycle-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, however, the material is not limited thereto.
The electron transport layer may function to facilitate electron transport. The electron transport material is a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. Specific examples thereof include: al complexes of 8-hydroxyquinoline; a complex comprising Alq 3; an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The thickness of the electron transport layer may be 1nm to 50 nm. The electron transport layer having a thickness of 1nm or more has an advantage of preventing the electron transport property from being degraded, and the electron transport layer having a thickness of 50nm or less has an advantage of preventing the driving voltage for enhancing electron transfer from being increased due to the electron transport layer being too thick.
The electron injection layer may function to promote electron injection. The electron-injecting material is preferably a compound of: it has an ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injection layer, and, in addition, has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
As the cathode material, a material having a small work function is generally preferred so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials, such as LiF/Al or LiO 2/Al; and the like, but are not limited thereto.
The organic electroluminescent device provided by the invention can be applied to Organic Light Emitting Devices (OLEDs), Organic Solar Cells (OSCs), electronic paper (e-paper), Organic Photoreceptors (OPC) or Organic Thin Film Transistors (OTFTs).
The invention provides a luminescent auxiliary material containing triarylamine functional groups, a preparation method thereof and an organic electroluminescent device. The organic electroluminescent auxiliary material greatly improves the hole transmission efficiency and the electron blocking capability, and the charge balance of holes and electrons in the luminescent layer is increased, so that the luminescent layer is not arranged on the surface of the hole transport layer, but well formed in the luminescent layer, and the maximization efficiency and the service life are judged. The introduction of structures such as benzo five-membered (hetero) rings, six-membered heterocycles and the like reduces the symmetry of molecules, increases conformational isomers of the molecules, has a rigid planar structure, is not easy to crystallize and aggregate among the molecules, and improves the yield of the manufactured organic EL elements. Therefore, the organic luminescent compound of the present invention can improve the characteristics of luminous efficiency, driving voltage, service life, etc. in an organic luminescent device.
The light-emitting auxiliary material provided by the invention can be used for producing an organic electroluminescent device with low driving voltage, high luminous efficiency and/or long service life.
The experimental result shows that compared with the existing organic electroluminescent device, the organic electroluminescent device prepared by using the luminescent auxiliary material provided by the invention has the advantages that the driving voltage is obviously reduced, and the luminous efficiency and the service life are obviously improved.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Synthesis of intermediate 1: under the protection of nitrogen, dissolving a raw material A-16(30.00mmol) and a raw material B-16(30.00mmol) in a 150.00ml toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.30mmol), tri-tert-butylphosphine (1.50mmol) and sodium tert-butoxide (60.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 1(10.93g, yield: 86.77%);
(2) synthesis of intermediate 2: under the protection of nitrogen, dissolving the intermediate 1(23.81mmol) and the raw material C-16(23.81mmol) in 180.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.24mmol), tri-tert-butylphosphine (1.19mmol) and sodium tert-butoxide (47.62mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Then dissolving the solid obtained by drying in a methanol solution, heating and stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching with petroleum ether, and drying to prepare an intermediate 2(15.31g, yield: 86.64%);
(3) synthesis of intermediate 3: under the protection of nitrogen, dissolving the intermediate 2(16.17mmol) and the raw material D-16(16.17mmol) in a mixed solution of 150.00ml of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding palladium tetratriphenylphosphine (0.16mmol) and potassium carbonate (32.34mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, slightly cooling after the reaction is finished, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 3(11.16g, yield: 84.58%);
(4) synthesis of compound 16: under the protection of nitrogen, dissolving intermediate 3(12.26mmol) and raw material E (12.26mmol) in 130.00ml of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding tetrakistriphenylphosphine palladium (0.12mmol) and potassium carbonate (24.52mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 10:4) to obtain compound-16 (8.89g, yield: 84.63%, Mw: 857.05).
The compound 16 thus obtained was subjected to assay, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 857.07; the test value was 857.05.
Elemental analysis:
the calculated values are: c, 89.69; h, 5.17; n, 3.27; o, 1.87.
The test values are: c, 89.68; h, 5.18; n, 3.28; o, 1.86.
Example 2
(1) Synthesis of intermediate 1: under the protection of nitrogen, dissolving a raw material A-45(30.00mmol) and a raw material B-45(30.00mmol) in 200.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.30mmol), tri-tert-butylphosphine (1.50mmol) and sodium tert-butoxide (60.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 1(15.66g, yield: 86.72%);
(2) synthesis of intermediate 2: under the protection of nitrogen, dissolving the intermediate 1(24.91mmol) and the raw material C-45(24.91mmol) in 220.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.25mmol), tri-tert-butylphosphine (1.25mmol) and sodium tert-butoxide (49.82mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Then dissolving the solid obtained by drying in a methanol solution, heating and stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching with petroleum ether, and drying to prepare an intermediate 2(18.32g, yield: 86.69%);
(3) synthesis of intermediate 3: under the protection of nitrogen, dissolving intermediate 2(17.68mmol) and raw material D-45(17.68mmol) in 170.00ml of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water is 3:1:1), adding tetratriphenylphosphine palladium (0.18mmol) and potassium carbonate (35.36mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, slightly cooling after the reaction is finished, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 3(12.63g, yield: 84.51%);
(4) synthesis of compound 45: dissolving intermediate 3(14.19mmol) and raw material E (14.19mmol) in 130.00ml of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1) under the protection of nitrogen, adding tetrakistriphenylphosphine palladium (0.14mmol) and potassium carbonate (28.38mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 10:4) to obtain compound-16 (11.92g, yield: 84.57%, Mw: 993.27).
The compound 45 thus obtained was subjected to assay, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 993.26; the test value was 993.27.
Elemental analysis:
the calculated values are: c, 84.65; h, 4.47; n, 2.82; o, 1.61; and S, 6.46.
The test values are: c, 84.66; h, 4.48; n, 2.81; o, 1.61; s, 6.45.
Example 3
(1) Synthesis of intermediate 1: under the protection of nitrogen, dissolving a raw material A-70(30.00mmol) and a raw material B-70(30.00mmol) in a 150.00ml toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.30mmol), tri-tert-butylphosphine (1.50mmol) and sodium tert-butoxide (60.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 1(13.61g, yield: 86.74%);
(2) synthesis of intermediate 2: under the protection of nitrogen, dissolving the intermediate 1(24.85mmol) and the raw material C-70(24.35mmol) in 180.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.25mmol), tri-tert-butylphosphine (1.24mmol) and sodium tert-butoxide (49.70mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Then dissolving the solid obtained by drying in a methanol solution, heating and stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching with petroleum ether, and drying to prepare an intermediate 2(15.95g, yield: 86.69%);
(3) synthesis of compound 70: under the protection of nitrogen, dissolving intermediate 2(13.51mmol) and raw material D-70(13.51mmol) in 130.00ml of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding palladium tetratriphenylphosphine (0.14mmol) and potassium carbonate (27.02mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 10:4) to obtain compound-16 (8.94g, yield: 84.66%, Mw: 782.03).
The detection analysis was performed on the obtained compound-70, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 782.00; the test value was 782.03.
Elemental analysis:
the calculated values are: c, 89.08; h, 5.54; n, 5.37.
The test values are: c, 89.07; h, 5.56; n, 5.36.
Example 4
(1) Synthesis of intermediate 1: under the protection of nitrogen, dissolving a raw material A-81(30.00mmol) and a raw material B-81(30.00mmol) in a 150.00ml toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.30mmol), tri-tert-butylphosphine (1.50mmol) and sodium tert-butoxide (60.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 1(15.10g, yield: 86.74%);
(2) synthesis of intermediate 2: under the protection of nitrogen, dissolving the intermediate 1(25.85mmol) and the raw material C-81(25.85mmol) in 220.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.26mmol), tri-tert-butylphosphine (1.29mmol) and sodium tert-butoxide (51.70mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining the organic phase, and then extracting the aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Then dissolving the solid obtained by drying in a methanol solution, heating and stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching with petroleum ether, and drying to prepare an intermediate 2(18.52g, yield: 86.71%);
(3) synthesis of intermediate 3: under the protection of nitrogen, dissolving the intermediate 2(12.10mmol) and the raw material D-81(12.10mmol) in a mixed solution of 120.00ml of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding palladium tetratriphenylphosphine (0.12mmol) and potassium carbonate (21.20mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, slightly cooling after the reaction is finished, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to prepare an intermediate 3(8.42g, yield: 84.53%);
(4) synthesis of compound 81: under the protection of nitrogen, dissolving intermediate 3(9.71mmol) and raw material E-81(9.71mmol) in 100.00ml of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding tetrakistriphenylphosphine palladium (0.10mmol) and potassium carbonate (19.42mmol), stirring uniformly, heating to 90 ℃, and refluxing for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: V ═ 10:4) to obtain compound-81 (8.06g, yield: 84.60%, Mw: 981.30).
The compound 81 thus obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 981.31; the test value was 981.30.
Elemental analysis:
the calculated values are: c, 88.13; h, 5.75; n, 2.85; and S, 3.27.
The test values are: c, 88.14; h, 5.76; n, 2.84; and S, 3.26.
The general structural formula is formula I in the summary of the invention, and the synthetic routes and principles of other compounds are the same as those of the above-listed examples, so the description is not exhaustive.
The compounds synthesized in the above examples were tested for their glass transition temperature (tg) using TMA4000, as shown in table 1:
TABLE 1
Compound (I)
Glass transition temperature (tg)
Compound (I)
Glass transition temperature (tg)
3
174.2
45
168.1
7
169.5
51
173.3
10
177.3
59
167.9
16
168.9
64
179.3
19
173.7
70
174.8
23
170.1
75
171.6
30
179.5
77
178.6
35
172.8
81
175.2
40
174.4
84
172.7
As can be seen from table 1, the hole transport material of the present disclosure has better thermal stability.
When the organic layer includes the light-emitting auxiliary layer, the light-emitting auxiliary layer includes the light-emitting auxiliary material provided in the above embodiment.
Device example 1
The embodiment provides a method for manufacturing an organic electroluminescent device, which includes the steps of:
the ITO glass substrate with the coating thickness of 150nm is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times and ultrasonic cleaning is carried out for 10 minutes, after the cleaning of the distilled water is finished, solvents such as isopropanol, acetone and methanol are sequentially subjected to ultrasonic cleaning and then dried, the ITO glass substrate is transferred to a plasma cleaning machine, the ITO glass substrate is cleaned for 5 minutes, and the ITO glass substrate is sent to an evaporation machine.
Firstly, evaporating a hole injection layer material HAT-CN on the ITO anode layer in a vacuum evaporation mode, wherein the thickness is 10 nm; vacuum evaporating 15nm of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) on the hole injection layer to form a hole transport layer; vacuum evaporation of 95nm of the compound 16 provided in example 1 above as a light-emitting auxiliary layer on top of the hole transport layer; then, a main material ADN and a doping material Ir (PPy) with the thickness of 40nm are evaporated on the light-emitting auxiliary layer in vacuum2(acac) as a light-emitting layer, wherein the weight ratio of the host material to the dopant material is 97: 3; then, TPBi and Liq with the thickness of 35nm are subjected to vacuum evaporation on the light-emitting layer to form an electron transport layer, wherein the weight ratio of the TPBi to the Liq is 60: 40; vacuum evaporating Yb with the thickness of 1nm on the electron transport layer to form an electron injection layer; finally, performing vacuum evaporation on the electron injection layer to form magnesium and silver as cathodes, wherein the weight ratio of the magnesium to the silver is 1:9, and the evaporation thickness is 18 nm; and (3) performing vacuum evaporation on the cathode to obtain IDX001 with the thickness of 70nm as a light extraction layer, thus obtaining the organic electroluminescent device.
By referring to the method provided in device example 1 above, compounds 3, 7, 10, 19, 23, 30, 35, 40, 45, 51, 59, 64, 70, 75, 77, 81, and 84 were selected instead of compound 16, respectively, and evaporation of the light-emitting auxiliary layer was performed to prepare corresponding organic electroluminescent devices, which are denoted as device examples 2 to 18, respectively.
Device comparative example 1:
this comparative example provides an organic electroluminescent device whose preparation process differs from that of device example 1 only in that the organic electroluminescent device was evaporated using the existing comparative compound a instead of the light-emitting auxiliary material (compound 1) in device example 1 described above. Wherein the chemical structural formula of comparative compound a is:
the organic electroluminescent devices obtained in the above device examples 1 to 18 and device comparative example 1 were characterized at a luminance of 15000(nits) for driving voltage, luminous efficiency and lifetime, and the test results are shown in the following table 2:
TABLE 2
As can be seen from table 2, the organic electroluminescent device prepared using the light-emitting auxiliary material provided by the present invention has a significantly reduced driving voltage and significantly improved luminous efficiency and lifetime compared to the conventional organic electroluminescent device provided in comparative example 1.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
