CN112480011B - Nitrogen-containing compound, organic electroluminescent device, and electronic device - Google Patents
Nitrogen-containing compound, organic electroluminescent device, and electronic device Download PDFInfo
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- CN112480011B CN112480011B CN202011412194.8A CN202011412194A CN112480011B CN 112480011 B CN112480011 B CN 112480011B CN 202011412194 A CN202011412194 A CN 202011412194A CN 112480011 B CN112480011 B CN 112480011B
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Abstract
The application relates to the technical field of organic electroluminescent materials, and provides a nitrogen-containing compound shown in chemical formula 1, an organic electroluminescent device and an electronic device. The nitrogen-containing compound can improve the performance of the organic electroluminescent device.
Description
Technical Field
The application relates to the technical field of organic electroluminescent materials, in particular to a nitrogen-containing compound, an organic electroluminescent device and an electronic device.
Background
With the development of electronic technology and the progress of material science, the application range of organic electroluminescent devices for realizing electroluminescence is more and more extensive. An organic electroluminescent device generally includes a cathode and an anode that are oppositely disposed, and a functional layer disposed between the cathode and the anode. The functional layer is composed of a plurality of organic or inorganic film layers and generally comprises an organic light-emitting layer, a hole transport layer positioned between the organic light-emitting layer and an anode, and an electron transport layer positioned between the organic light-emitting layer and a cathode. When voltage is applied to the anode and the cathode, the two electrodes generate an electric field, electrons on the cathode side move to the organic light emitting layer under the action of the electric field, holes on the anode side also move to the light emitting layer, the electrons and the holes are combined in the organic light emitting layer to form excitons, and the excitons are in an excited state and release energy outwards, so that the organic light emitting layer emits light outwards.
Currently, the organic electroluminescent device still has shortcomings in terms of driving voltage, light emitting efficiency, device lifetime, and other properties, and it is necessary to continuously develop new materials to further improve the properties of the organic electroluminescent device.
The above information disclosed in this background section is only for enhancement of understanding of the background of the disclosure and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
An object of the present application is to provide a nitrogen-containing compound, an organic electroluminescent device, and an electronic apparatus, which improve the performance of the organic electroluminescent device.
In order to achieve the purpose, the technical scheme adopted by the disclosure is as follows:
according to a first aspect of the present application, there is provided a nitrogen-containing compound having a structural formula shown in chemical formula 1:
wherein, X 1 And X 2 Are the same or different and are each independently selected from C (H) or N;
Ar 1 、Ar 2 and Ar 3 The same or different, and each is independently selected from substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted heteroaryl with 3-30 carbon atoms;
Ar 1 、Ar 2 and Ar 3 Wherein the substituent is selected from deuterium, halogen group, cyano, halogenated alkyl with 1-10 carbon atoms, deuterated alkyl with 1-10 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkylthio with 1-10 carbon atoms, trialkylsilyl with 3-12 carbon atoms, aryl with 6-20 carbon atoms, heteroaryl with 3-18 carbon atoms, aryloxy with 6-18 carbon atoms, arylthio with 6-18 carbon atoms and triarylsilyl with 18-24 carbon atoms; optionally, any two adjacent substituents form a ring.
According to a second aspect of the present application, there is provided an organic electroluminescent device comprising an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; the functional layer comprises the nitrogen-containing compound described above.
According to a third aspect of the present application, there is provided an electronic apparatus comprising the above-described organic electroluminescent device.
The nitrogen-containing compound provided by the application comprises phenanthrene/mono-azaphenanthrene/bis-azaphenanthrene (phenanthroline) benzimidazole group, and the group is connected with an arylamine structure through an adamantane spirofluorene bridging group. The large plane conjugated system of phenanthrene/mono-azaphenanthrene/bis-azaphenanthrene (phenanthroline) imidazole group has electron transport performance, and the arylamine structure has hole transport performance. This makes the nitrogen-containing compound of the present application a bipolar material, which can have both good electron transport ability and hole transport ability. When the nitrogen-containing compound is applied to an organic light-emitting layer of an organic electroluminescent device, the recombination rate of holes and electrons in the organic light-emitting layer can be improved, and the light-emitting efficiency of the organic electroluminescent device is further improved. Furthermore, the nitrogen-containing compound has the highest occupied orbital (HOMO) distributed on the arylamine structure and the lowest unoccupied orbital (LUMO) distributed on the phenanthrene/monoazaphenanthrene/disazaphenanthrene (phenanthroline) benzimidazole group, with the highest occupied orbital and the lowest unoccupied orbital having a greater coincidence on the adamantane spirofluorene bridging group. This causes the first excited singlet state of the nitrogen-containing compound to assume the characteristic of a hybrid local-charge transfer excited state (HLCT); on one hand, stronger fluorescence emission can be realized, on the other hand, triplet excitons can be more fully utilized, and the luminous efficiency of the organic electroluminescent device is further improved. In addition, the adamantyl group on the adamantine spirofluorene bridging group has large space volume and strong rigidity, so that the intermolecular interaction force of the nitrogen-containing compounds can be reduced, and pi-pi stacking among molecules is inhibited, so that the nitrogen-containing compounds have higher glass transition temperature, the film forming property of the nitrogen-containing compounds is improved, and the service life of an organic electroluminescent device is prolonged.
Drawings
The above and other features and advantages of the present application will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present application.
Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
The reference numerals of the main elements in the figures are explained as follows:
100. an anode; 200. a cathode; 300. a functional layer; 310. a hole injection layer; 321. a hole transport layer; 322. an electron blocking layer; 330. an organic light-emitting layer; 340. an electron transport layer; 350. an electron injection layer; 400. an electronic device.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the application.
In the drawings, the thickness of regions and layers may be exaggerated for clarity. The same reference numerals denote the same or similar structures in the drawings, and thus detailed descriptions thereof will be omitted.
The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to give a thorough understanding of embodiments of the application. One skilled in the relevant art will recognize, however, that the subject matter of the present application can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring major technical ideas of the application.
The terms "comprising" and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc.
In the present application, the term "substituted or unsubstituted" means that a functional group described later in the term may or may not have a substituent (hereinafter, for convenience of description, the substituent is collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. The substituent Rc may be, for example, deuterium, a halogen group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a deuterated alkyl group, a cycloalkyl group, a trialkylsilyl group, a triphenylsilyl group, a diarylphosphinyl group, an aryloxy group, or the like. In the present application, a "substituted" functional group may be substituted with 1 or 2 or more substituents Rc as described above.
In the present application, "any two adjacent substituents form a ring," any adjacent "may include two substituents on the same atom, and may also include one substituent on each of two adjacent atoms; wherein, when two substituents are present on the same atom, both substituents may form a saturated or unsaturated ring with the atom to which they are both attached; when two adjacent atoms have a substituent on each, the two substituents may be fused to form a ring.
In the present application, the number of carbon atoms of a substituted or unsubstituted group refers to all the number of carbon atoms. For example, if Ar 1 Is a substituted aryl group having 12 carbon atoms, all of the carbon atoms of the aryl group and the substituents thereon are 12.
The descriptions used in this application that "… … independently" and "… … independently" and "… … independently selected from" are interchangeable and should be understood in a broad sense to mean that the particular items expressed between the same symbols do not interfere with each other in different groups or that the particular items expressed between the same symbols do not interfere with each other in the same groups. For example: in "
Wherein each q is independently 0, 1,2 or 3, and each R "is independently selected from the group consisting of hydrogen, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' exist on a benzene ring, each R ' can be the same or different, and the options of each R ' do not influence each other; the formula Q-2 represents the phenyl ring of biphenyl having Q substituents R 'on each phenyl ring, and one of the R' substituents on two phenyl ringsThe number q may be the same or different, and each R 'may be the same or different, and the options of each R' are not affected.
In this application, the terms "optional" and "optionally" mean that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "optionally, any two adjacent substituents x form a ring; "means that these two substituents may but need not form a ring, including: a case where two adjacent substituents form a ring and a case where two adjacent substituents do not form a ring.
In the present application, aryl refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group can be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aryl group can be a monocyclic aryl group, a fused ring aryl group, two or more monocyclic aryl groups joined by carbon-carbon bond conjugation, monocyclic aryl and fused ring aryl groups joined by carbon-carbon bond conjugation, two or more fused ring aryl groups joined by carbon-carbon bond conjugation. That is, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered an aryl group herein. The fused ring aryl group may include, for example, a bicyclic fused aryl group (e.g., naphthyl group), a tricyclic fused aryl group (e.g., phenanthryl group, fluorenyl group, anthracyl group), and the like. The aryl group does not contain a hetero atom such as B, N, O, S, Se, Si or P. For example, biphenyl, terphenyl, and the like are aryl groups in this application. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, benzo [9,10 ]]Phenanthryl, pyrenyl, benzofluoranthenyl, phenanthrenyl, pyrenyl,
an indenyl group, etc., without being limited thereto.
In the present application, a substituted aryl group may be one in which one or two or more hydrogen atoms are substituted by a group such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, alkoxy, alkylthio, etc. Specific examples of heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, pyridinyl-substituted phenyl, carbazolyl-substituted phenyl, and the like. It is understood that the number of carbon atoms of a substituted aryl group, as used herein, refers to the total number of carbon atoms in the aryl group and the substituents on the aryl group, e.g., a substituted aryl group having a carbon number of 18, refers to a total carbon number of 18 in the aryl group and the substituents.
In the present application, the fluorenyl group may be substituted and two substituents may be combined with each other to form a spiro structure, and specific examples include, but are not limited to, the following structures:
in the present application, heteroaryl means a monovalent aromatic ring containing at least one heteroatom, which may be at least one of B, O, N, P, Si, Se and S, in the ring or a derivative thereof. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. Exemplary heteroaryl groups can include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, and N-arylcarbazolyl (e.g., N-phenylcarbazolyl), N-heteroarylcarbazolyl (e.g., N-pyridylcarbazolyl), N-alkyl carbazolyl groups (e.g., N-methyl carbazolyl group), etc., without being limited thereto. Wherein, thienyl, furyl, phenanthroline group and the like are heteroaryl of a single aromatic ring system type, and N-aryl carbazolyl and N-heteroaryl carbazolyl are heteroaryl of a polycyclic system type connected by carbon-carbon bond conjugation.
In the present application, substituted heteroaryl groups may be heteroaryl groups in which one or more hydrogen atoms are substituted with groups such as deuterium atoms, halogen groups, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, cycloalkyl, alkoxy, alkylthio, and the like. Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothiophenyl, phenyl-substituted pyridyl, and the like. It is understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituent on the heteroaryl group.
In this application, an delocalized linkage refers to a single bond extending from a ring system
It means that one end of the linkage may be attached to any position in the ring system through which the linkage extends, and the other end to the rest of the compound molecule.
For example, as shown in formula (f), naphthyl represented by formula (f) is connected to other positions of the molecule through two non-positioned bonds penetrating through the bicyclic ring, and the meaning of the naphthyl represented by the formula (f-1) to the naphthyl represented by the formula (f-10) includes any possible connection mode.
As another example, as shown in the following formula (X '), the phenanthryl group represented by formula (X') is bonded to other positions of the molecule through an delocalized bond extending from the middle of the phenyl ring on one side, and the meanings represented thereby include any of the possible bonding modes as shown in formulas (X '-1) to (X' -4).
An delocalized substituent, as used herein, refers to a substituent attached by a single bond extending from the center of the ring system, meaning that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' group represented by the formula (Y) is bonded to the quinoline ring via an delocalized bond, and the meaning thereof includes any of the possible bonding modes as shown in the formulae (Y-1) to (Y-7).
The application provides a nitrogen-containing compound, wherein the structural formula of the nitrogen-containing compound is shown in chemical formula 1:
wherein X 1 And X 2 Are the same or different and are each independently selected from C (H) or N;
Ar 1 、Ar 2 and Ar 3 The same or different, and each is independently selected from substituted or unsubstituted aryl with 6-30 carbon atoms, substituted or unsubstituted heteroaryl with 3-30 carbon atoms;
Ar 1 、Ar 2 and Ar 3 Wherein the substituent is selected from deuterium, a halogen group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, and a triarylsilyl group having 18 to 24 carbon atoms; optionally, any two adjacent substituents form a ring.
In the present application, the alkyl group having 1 to 10 carbon atoms may include a straight-chain alkyl group having 1 to 10 carbon atoms and a branched-chain alkyl group having 3 to 10 carbon atoms. The number of carbon atoms may be, for example, 1,2, 3,4, 5,6, 7, 8, 9, 10. Specific examples of the alkyl group having 1 to 10 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-dimethyloctyl, and the like.
In the present application, the halogen group may include fluorine, bromine, chlorine, iodine, and the like.
In the present application, the aryl group as a substituent has 6 to 20 carbon atoms, and the number of carbon atoms may be, for example, 6, 10, 12, 14, 15, 16, 18, or the like. Specific examples of the aryl group as the substituent include, but are not limited to, phenyl, naphthyl, biphenyl, dimethylfluorenyl, anthryl, phenanthryl and the like.
In the present application, the heteroaryl group as a substituent has 3 to 18 carbon atoms, and the number of carbon atoms may be, for example, 3,4, 5, 7, 8, 9, 12, 18, or the like. Specific examples of heteroaryl as a substituent include, but are not limited to, pyridyl, quinolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, and the like.
In the present application, specific examples of the trialkylsilyl group having 3 to 12 carbon atoms include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and the like.
In the present application, specific examples of the cycloalkyl group having 3 to 10 carbon atoms include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, and the like.
According to one embodiment, X 1 And X 2 And is C (H). According to another embodiment, X 1 And X 2 One or both of which are N.
Optionally, the structural formula of the nitrogen-containing compound is any one of the following chemical formulas:
alternatively, Ar 1 、Ar 2 And Ar 3 Wherein the substituents are each independently selected from deuterium,A halogen group, a cyano group, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a trialkylsilyl group having 3 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, and a triphenylsilyl group.
Alternatively, Ar 1 And Ar 2 The same or different, and each is independently selected from substituted or unsubstituted aryl with 6-25 carbon atoms or substituted or unsubstituted heteroaryl with 5-20 carbon atoms.
For example, Ar 1 And Ar 2 Each independently selected from substituted or unsubstituted aryl groups having 6, 7, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 24, 25 carbon atoms or from substituted or unsubstituted heteroaryl groups having 5, 8, 9, 12, 14, 16, 18, 20 carbon atoms.
Preferably, Ar 1 And Ar 2 The same or different, and each is independently selected from substituted or unsubstituted aryl with 6-15 carbon atoms or substituted or unsubstituted heteroaryl with 8-15 carbon atoms.
Alternatively, Ar 1 And Ar 2 Wherein the substituents are independently selected from deuterium, fluorine, cyano, C1-4 alkyl, C1-4 alkoxy, C1-4 alkylthio, C1-4 fluoroalkyl, C1-4 deuterated alkyl, C5-10 cycloalkyl, C6-12 aryl, C5-12 heteroaryl, C3-7 trialkylsilyl, and triphenylsilyl.
For example, Ar 1 And Ar 2 Specific examples of the substituent in (1) include, but are not limited to, deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trideuteromethyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, naphthyl, dibenzofuranyl, dibenzo, and the likeThienyl, pyridyl, quinolyl, trimethylsilyl and the like.
In some embodiments, Ar 1 And Ar 2 Are the same or different and are each independently selected from the group consisting of groups represented by formula i-1 through formula i-14: and each independently selected from the group consisting of groups represented by formulas i-1 through i-14:
wherein M is 1 Selected from a single bond or
G 1 ～G 5 Each independently selected from N or C (F) 1 ) And G is 1 ～G 5 At least one is selected from N; when G is 1 ～G 5 Two or more selected from C (F) 1 ) When, two arbitrary F 1 The same or different;
G 6 ～G 13 each independently selected from N or C (F) 2 ) And G is 6 ～G 13 At least one is selected from N; when G is 6 ～G 13 Two or more of C (F) 2 ) When, two arbitrary F 2 The same or different;
G 14 ～G 23 each independently selected from N or C (F) 3 ) And G is 14 ～G 23 At least one is selected from N; when G is 14 ～G 23 Two or more of C (F) 3 ) When, two arbitrary F 3 The same or different;
H 1 selected from deuterium, fluorine, chlorine, bromine, cyano-group, trialkylsilyl group having 3-12 carbon atoms, alkyl group having 1-10 carbon atoms, halogenated alkyl group having 1-10 carbon atoms, deuterated alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, alkoxy group having 1-10 carbon atoms, alkylthio group having 1-10 carbon atoms and triphenylsilyl group;
H 2 ～H 9 、H 21 each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3-12 carbon atoms, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, deuterated alkyl having 1-10 carbon atoms, cycloalkyl having 3-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, heteroaryl having 3-18 carbon atoms, and triphenylsilyl;
H 10 ～H 20 、F 1 ～F 3 each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3-12 carbon atoms, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, deuterated alkyl having 1-10 carbon atoms, cycloalkyl having 3-10 carbon atoms, alkoxy having 1-10 carbon atoms, alkylthio having 1-10 carbon atoms, aryl having 6-18 carbon atoms, heteroaryl having 3-18 carbon atoms, and triphenylsilyl;
h 1 ～h 21 in h is given by k Is represented by H 1 ～H 21 With H k Is represented by k is a variable and represents an arbitrary integer of 1 to 21, h k Represents a substituent H k The number of (2); wherein, when k is selected from 5 or 17, h k Selected from 1,2 or 3; when k is selected from 2, 7, 8, 12, 15, 16, 18 or 21, h k Selected from 1,2, 3 or 4; when k is selected from 1, 3,4, 6, 9 or 14, h k Selected from 1,2, 3,4 or 5; when k is 13, h k Selected from 1,2, 3,4, 5 or 6; when k is selected from 10 or 19, h k Selected from 1,2, 3,4, 5,6 or 7; when k is 20, h k Selected from 1,2, 3,4, 5,6, 7 or 8; when k is 11, h k Selected from 1,2, 3,4, 5,6, 7, 8 or 9; and when h is k When greater than 1, any two H k The same or different; optionally, any two adjacent H k Forming a ring;
K 1 selected from O, S, Se, N (H) 22 )、C(H 23 H 24 )、Si(H 23 H 24 ) (ii) a Wherein H 22 、H 23 、H 24 Each independently of the otherIs selected from: an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or the above H 23 And H 24 Are linked to each other to form, together with the atoms to which they are commonly linked, a 5-to 18-membered saturated or unsaturated ring;
K 2 selected from single bond, O, S, Se, N (H) 25 )、C(H 26 H 27 )、Si(H 26 H 27 ) (ii) a Wherein H 25 、H 26 、H 27 Each independently selected from: an aryl group having 6 to 18 carbon atoms, a heteroaryl group having 3 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or the above H 26 And H 27 Are linked to form, together with the atoms to which they are commonly attached, a 5-to 18-membered saturated or unsaturated ring.
In the chemical formulae i-13 and i-14, F 2 To F 3 Can be expressed as F j Wherein j is a variable, and represents 2 or 3. For example, when j is 2, F j Is referred to as F 2 . It is to be understood that when the delocalized bond is attached to c (Fj), Fj in c (Fj) is absent. For example, in the chemical formula i-13, when
Is connected to G 12 When, G 12 The structure of formula i-13, which represents only C atoms, is specifically:
in the present application, the above-mentioned H 23 And H 24 H above 26 And H 27 In both groups, the ring formed by the interconnection of the two groups in each group may be saturated or unsaturated, for example a saturated or unsaturated 3 to 13 membered ring may be formed. For example, in the formula i-10, when K is 2 And M 1 Are all single bonds, H 19 Is hydrogen, and K 1 Is C (H) 23 H 24 ) When H is present 23 And H 24 Form of atoms linked to each other to be commonly bound to themWhen the five-membered ring is represented by the formula i-10
Likewise, the formula i-10 can also be represented
I.e. H 23 And H 24 The atoms that are linked to each other to be commonly bound to them form a partially unsaturated 13-membered ring.
Alternatively, Ar 1 And Ar 2 Identical or different and are each independently selected from substituted or unsubstituted radicals W 1 Wherein the unsubstituted radical W 1 Selected from the group consisting of:
substituted radicals W 1 Including one or more substituents independently selected from deuterium, fluoro, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, trifluoromethyl, trideuteromethyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl. When substituted group W 1 Wherein when the number of the substituents is 2 or more, any two of the substituents may be the same or different from each other, and any two adjacent substituents may or may not form a ring.
Further optionally, Ar 1 And Ar 2 The same or different, and each is independently selected from the group consisting of:
alternatively, Ar 3 Selected from substituted or unsubstituted aryl or carbon with 6-18 carbon atomsA substituted or unsubstituted heteroaryl group having 5 to 15 atoms.
For example, Ar 3 Selected from substituted or unsubstituted aryl groups having 6, 7, 10, 12, 13, 14, 15, 16, 17, 18 carbon atoms, or selected from substituted or unsubstituted heteroaryl groups having 5, 8, 9, 12, 14, 15 carbon atoms.
Preferably, Ar 3 Selected from substituted or unsubstituted aryl with 6-12 carbon atoms or substituted or unsubstituted heteroaryl with 8-12 carbon atoms.
Alternatively, Ar 3 Wherein the substituents are independently selected from deuterium, fluorine, cyano, C1-4 alkyl, C1-4 fluoroalkyl, C1-4 deuterated alkyl, C5-10 cycloalkyl, C6-12 aryl, and C3-7 trialkylsilyl.
For example, Ar 3 Specific examples of the substituent in (1) include, but are not limited to, deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trideuteromethyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl and the like.
Alternatively, Ar 3 Selected from substituted or unsubstituted groups W 2 Wherein the unsubstituted group W 2 Selected from the group consisting of:
substituted radicals W 2 Including one or more substituents independently selected from deuterium, fluoro, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trideuteromethyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl. When substituted group W 2 Wherein when the number of the substituents is 2 or more, any two of the substituents may be the same or different from each other, and any two adjacent substituents may or may not form a ring.
Further optionally, Ar 3 Selected from the group consisting of:
in one embodiment, Ar 1 、Ar 2 And Ar 3 The number of carbon atoms in the carbon-containing resin is 15 or more. Therefore, the nitrogen-containing compound has more proper molecular weight, the over-high evaporation temperature of the nitrogen-containing compound is avoided, the decomposition of the nitrogen-containing compound during evaporation is avoided, and the mass production stability of the organic electroluminescent device is further improved.
In a preferred embodiment, in chemical formula 1, X 1 And X 2 In this case, the nitrogen-containing compound of the present application is applied to an organic electroluminescent device, which can further improve the photoelectric efficiency of the device.
Alternatively, the nitrogen-containing compound of the present application is selected from the group consisting of:
the present application also provides an organic electroluminescent device, as shown in fig. 1, the organic electroluminescent device includes an anode 100 and a cathode 200 oppositely disposed, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 comprises a nitrogen-containing compound as provided herein.
Alternatively, the functional layer 300 includes an organic light emitting layer 330 including the nitrogen-containing compound of the present application. The nitrogen-containing compound has good electron transport capability and hole transport capability, so that the recombination rate of holes and electrons in the organic light-emitting layer 330 can be improved, and the light-emitting efficiency of the organic electroluminescent device is further improved. The adamantyl group of the nitrogen-containing compound has large space volume and strong rigidity, and can reduce intermolecular interaction force and inhibit intermolecular pi-pi stacking, so that the nitrogen-containing compound has higher glass transition temperature, the film forming property of the nitrogen-containing compound is improved, and the service life of an organic electroluminescent device is prolonged.
Alternatively, the organic light emitting layer 330 includes a host material and a guest material (i.e., dopant) including the nitrogen-containing compound of the present application. The nitrogen-containing compound has a greater coincidence of the highest occupied orbital and the lowest unoccupied orbital on the adamantane spirofluorene bridging group. This causes the first excited singlet state of the nitrogen-containing compound to exhibit the characteristics of HLCT; on one hand, stronger fluorescence emission can be realized, on the other hand, triplet excitons can be more fully utilized, and the luminous efficiency of the organic electroluminescent device is further improved.
The host material of the organic light emitting layer 330 may be an anthracene derivative, a metal chelate compound, a bis-styryl derivative, an aromatic amine derivative, a dibenzofuran derivative, or other types of materials, which is not particularly limited in the present application. In one embodiment of the present application, the host material of the organic light emitting layer 330 may be α, β -ADN.
Optionally, the functional layer 300 may further include a hole transport layer 321, and the hole transport layer 321 is disposed between the organic light emitting layer 330 and the anode 100 to enhance the capability of the anode 100 to inject holes into the organic light emitting layer. The material of the hole transport layer 321 may be selected from phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, benzidine triarylamine, diamine triarylamine, or other types of materials, which are not limited in this application. In one embodiment of the present application, the material of the hole transport layer 321 may be NPAPF.
Optionally, the functional layer 300 may further include an electron blocking layer 322, and the electron blocking layer 322 is interposed between the hole transport layer 321 and the organic light emitting layer 330 to improve the transport of blocking electrons to the anode direction and improve the recombination rate of electrons and holes in the organic light emitting layer 330. The material of the electron blocking layer 322 may be selected from diamine type triarylamine, styrene amine type triarylamine, or other types of materials, which are not particularly limited in this application. In one embodiment of the present application, the material of the electron blocking layer 322 may be α, β -TNB.
Alternatively, as shown in fig. 1, the functional layer 300 may further include a hole injection layer 310, and the hole injection layer 310 is disposed between the anode 100 and the hole transport layer 321 to enhance the ability to inject holes into the hole transport layer 321. The hole injection layer 310 may be made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, polyaza-triphenylene compounds, or other materials, which is not limited in this application. In one embodiment of the present application, the hole injection layer 310 may be composed of HAT-CN.
Optionally, as shown in fig. 1, the functional layer 300 may further include an electron transport layer 340, and the electron transport layer 340 is disposed between the organic light emitting layer 330 and the cathode 200. The electron transport layer 340 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials, and the electron transport material may be selected from benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials, which is not limited in this application. In one embodiment of the present application, the electron transport layer 340 may be formed of BP 4 mPy and LiQ.
Optionally, as shown in fig. 1, the functional layer 300 may further include an electron injection layer 350, and the electron injection layer 350 is disposed between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic material. In one embodiment of the present application, the electron injection layer 350 may include Mg and LiF.
Optionally, the anode 100 comprises an anode material, preferably a material with a large work function that facilitates hole injection into the functional layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO, Al or SnO 2 Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.
Optionally, the cathode 200 comprises a cathode material, which is a material with a small work function that facilitates electron injection into the functional 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; or a multilayer material such as LiF/Al, Liq/Al, LiO 2 /Al、LiF/Ca、LiF/Al and BaF 2 But not limited thereto,/Ca. Preferably, a metal electrode comprising an Mg-Ag alloy is included as a cathode.
The application also provides an electronic device which comprises the organic electroluminescent device. As shown in fig. 2, the electronic device 400 may be, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices, which may include, but are not limited to, a computer screen, a mobile phone screen, a television, electronic paper, an emergency light, a light module, and the like. Since the electronic device has the organic electroluminescent device, the electronic device has the same beneficial effects, and the details are not repeated.
Hereinafter, the present application will be described in further detail with reference to examples. However, the following examples are merely illustrative of the present application and do not limit the present application.
Process for producing nitrogen-containing compound
The nitrogen-containing compound is obtained by the following synthetic route:
performing reflux reaction on the sub A-I, the sub B-I and the sub C-I in glacial acetic acid to obtain a target compound.
Wherein the synthetic route of sub B-I is as follows:
the synthesis steps are as follows:
(1) aldehyde group substituted o-bromoiodobenzene (raw materials a-i) and glycol are catalyzed by p-toluenesulfonic acid in a toluene solvent to protect aldehyde group and generate an intermediate b-i. Wherein the starting materials a-i can be synthesized via a two-step reaction with methoxycarbonyl-substituted o-bromoiodobenzene as a commercially available starting material with reference to CN 103517907A.
(2) Intermediate b-i and Chlorobenzeneboronic acid via Pd (PPh) 3 ) 4 Carrying out catalytic Suzuki reaction to generate an intermediate c-i;
(3) processing the intermediate c-i by n-butyl lithium at low temperature to generate an organic lithium reagent, and performing carbonyl addition reaction on the organic lithium reagent and a carbonyl group of the adamantanone to generate tertiary alcohol, namely an intermediate d-i;
(4) the intermediate d-i is catalyzed by concentrated sulfuric acid to close the ring in a glacial acetic acid solvent, and the protecting group is removed to generate an intermediate e-i;
(5) and carrying out Buchwald reaction on the intermediate e-I and diaryl substituted amine to generate sub B-I.
Specific synthesis examples are as follows:
1. synthesis of intermediates b-i:
into a 500mL three-necked flask equipped with a water separator, the starting material a-1(31.09g, 100mmol), ethylene glycol (12.42g, 200mmol), p-toluenesulfonic acid (1.72g, 10mmol) and toluene (310mL) were added in this order, stirring and heating were started, and the temperature was raised to reflux for 16 h. After the system is cooled to room temperature, pouring the reaction solution into saturated sodium bicarbonate aqueous solution (70mL), and fully stirring for 30 min; extracting with dichloromethane (150mL × 3), drying the organic phase with anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent to obtain a crude product; purification by column chromatography on silica gel using n-heptane/dichloromethane as the mobile phase gave the product intermediate b-1 as a pale yellow oil (32.66 g; yield 92%).
The structures of intermediates b-2, a-2 and b-2, and the yields thereof, which were synthesized using a-2 in a similar manner with reference to the synthesis of intermediate b-1, are shown in Table 1.
Table 1: synthesis of intermediate b-1 to intermediate i-1
2. Synthesis of intermediates c-i:
adding the intermediate b-1(32.66g, 92mmol), 4-chlorobenzeneboronic acid (15.11g, 96.6mmol), tetrakis (triphenylphosphine) palladium (2.13g, 1.84mmol), potassium carbonate (26.70g, 193.2mmol) and tetrabutylammonium bromide (5.93 g; 18.4mmol) into a 500mL three-necked flask in turn, adding a mixed solvent of toluene (330mL), ethanol (80mL) and water (80mL), heating to 80 ℃ under the protection of nitrogen, and stirring for reaction for 8 hours; cooling to room temperature, stopping stirring, washing the reaction solution with water, separating an organic phase, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; purification by column chromatography on silica gel using n-heptane/as mobile phase gave the product intermediate c-1 as a white solid (21.87 g; yield 70%).
Using a similar procedure to the synthesis of intermediate c-1, intermediate c-2 to intermediate c-6 were synthesized using the compounds shown in b-i in Table 2 instead of intermediate b-1 and starting material i instead of 4-chlorobenzeneboronic acid, with the yields shown in Table 2.
Table 2: synthesis of intermediate c-2 to intermediate c-6
4. Synthesis of intermediate d-i
Adding the intermediate c-1(21.87g, 64.40mmol) and tetrahydrofuran (390mL) into a 1000mL three-neck flask, and cooling the system to-78 ℃ under the protection of nitrogen; under the condition of stirring, dropwise adding n-hexane solution (35.5mL, 71mmol) of n-butyllithium (2.0M), and after dropwise adding, keeping the temperature (-78 ℃) and stirring for 1 hour; keeping the temperature at minus 78 ℃, dropwise adding a tetrahydrofuran (50mL) solution of adamantanone (9.67g, 64.40mmol), keeping the temperature at minus 78 ℃ for 1 hour after dropwise adding, and naturally heating the system to room temperature; adding water into the system for quenching reaction, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the crude product was purified by column chromatography on silica gel using an n-heptane/dichloromethane system to give the product intermediate d-1 as a white solid (13.68 g; yield 50%).
Using a similar procedure to the synthesis of intermediate d-1, intermediates d-2 to d-6 were synthesized using c-i shown in Table 3 instead of intermediate c-1, with the yields shown in Table 3.
Table 3: synthesis of intermediate d-2 to intermediate d-6
4. Synthesis of intermediate e-i
Adding the intermediate d-1(13.68g, 32.20mmol) and glacial acetic acid (140mL) into a 250mL three-necked flask, slowly dropwise adding a solution of concentrated sulfuric acid (98%) (0.35mL, 6.44mmol) in acetic acid (10mL) under the protection of nitrogen, raising the temperature to 80 ℃ after the dropwise adding is finished, and stirring for 2 hours; when the system is cooled to room temperature, adding 100mL of deionized water into the reaction system, fully stirring for 1 hour, filtering, fully leaching a filter cake to be neutral by using water and ethanol, and drying to obtain a crude product; the crude product was purified by column chromatography on silica gel using an n-heptane/dichloromethane system to give intermediate e-1(7.86 g; yield, 70%) as a white solid.
Using a method similar to that for the synthesis of intermediate e-1, intermediates e-2 to e-6 were synthesized using d-i in Table 4 below instead of intermediate d-1, with the yields shown in Table 4.
Table 4: synthesis of intermediate e-2 to intermediate e-6
5. Synthesis of sub B-I
To a 250mL three-necked flask were added in the order intermediate e-1(7.86g, 22.54mmol), N-phenyl-4-dibenzofuran amine (6.14g, 23.67mmol), and tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 (ii) a 0.42g, 0.45mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (S-Phos; 0.37g, 0.90mmol), sodium tert-butoxide (4.55g, 47.34mmol) and toluene (120mL), and the reaction is refluxed and stirred at 110 ℃ for 6 hours under the protection of nitrogen; cooling the system to room temperature, pouring the reaction solution into 250mL of deionized water, extracting with dichloromethane (150mL multiplied by 3), combining organic phases, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the crude product was purified by silica gel column chromatography using an n-heptane/dichloromethane system to give sub B-1 as a white solid (10.31 g; yield, 80%).
Using a similar procedure as described above, intermediates sub B-2 to sub B-23 were synthesized using e-i in table 5 below instead of intermediate e-1 and reactant ii instead of N-phenyl-4-dibenzofuran amine, the yields of which are shown in table 5.
Table 5: synthesis of intermediates sub B-2 to sub B-23
Note: reactant ii can be obtained from an aromatic amine and the corresponding halide by Buchwald-Hartwig reaction.
6. Synthesis of Compounds
1, 10-phenanthroline-5, 6-dione (4.26g, 20.29mmol), intermediate sub B-1(11.6g, 20.29mmol), aniline (2.84g, 30.44mmol), ammonium acetate (7.82g, 101.45mmol) and glacial acetic acid (120mL) are sequentially added into a 250mL three-neck flask, and the mixture is heated to reflux and stirred for reaction for 24 hours under the protection of nitrogen; cooling to room temperature, stopping stirring, pouring the reaction solution into 250mL of water, and separating out a large amount of grey solid; performing suction filtration, and washing a filter cake to be neutral by using deionized water; dissolving the filter cake with dichloromethane, and adding anhydrous magnesium sulfate for drying; filtering, and distilling under reduced pressure to remove the solvent to obtain a crude product; purification by column chromatography on silica gel using n-heptane/dichloromethane as mobile phase gave the product compound 10 as a white solid (11.9 g; yield 70%). The nuclear magnetic data of the compound 10 was obtained, 1 H-NMR(CDCl 3 ,400MHz):δppm 9.26(d,2H),9.15(d,1H),8.70(d,1H),8.01(d,1H),7.82(dd,2H),7.60-7.57(m,2H),7.47-7.45(m,9H),7.36-7.28(m,3H),7.20(t,1H),7.15(d,1H),7.02(s,1H),6.90-6.85(m,3H),6.36-6.33(m,2H),2.91(d,2H),2.61(d,2H),2.42(s,1H),2.16(s,1H),1.90(s,2H),1.77(d,2H),1.69(d,2H),1.60(s,2H)。
the compounds of Table 6 were synthesized using similar methods as described above, using sub A-I instead of 1, 10-phenanthroline-5, 6-dione, sub B-I instead of sub B-1, sub C-I instead of aniline in Table 6 below:
table 6: compound and yield thereof
Wherein, nuclear magnetic data for compound 428: 1 H-NMR(CDCl 3 ,400MHz):δppm 8.66(d,1H),8.53(d,1H),8.41(d,1H),8.26(d,1H),8.16(d,1H),7.90(t,2H),7.67(d,1H),7.65-7.47(m,5H),7.44-7.37(m,3H),7.43(t,1H),7.40-7.32(m,4H),7.30-7.24(m,2H),7.13-7.10(m,2H),6.98(d,1H),6.93(t,1H),6.85(d,2H),6.80(d,1H),2.80(s,3H),2.61(d,2H),2.31(d,2H),1.96(s,1H),1.60(s,3H),1.47(d,2H),1.39(d,2H),1.30(s,2H)。
mass spectrometry analysis was performed on the above compounds and the data are shown in table 7:
table 7: mass spectrometric data for partial compounds
| Compound (I) | Mass spectrometry | Compound (I) | Mass spectrometry |
| Compound 10 | m/z＝838.4[M + H] + | Compound 47 | m/z＝798.4[M + H] + |
| Compound 21 | m/z＝824.4[M + H] + | Compound 108 | m/z＝900.4[M + H] + |
| Compound 43 | m/z＝854.3[M + H] + | Compound 162 | m/z＝848.4[M + H] + |
| Compound 60 | m/z＝864.4[M + H] + | Compound 282 | m/z＝838.4[M + H] + |
| Compound 168 | m/z＝928.4[M + H] + | Compound 337 | m/z＝866.4[M + H] + |
| Compound 221 | m/z＝914.4[M + H] + | Compound 414 | m/z＝898.4[M + H] + |
| Compound 237 | m/z＝824.4[M + H] + | Compound 428 | m/z＝810.4[M + H] + |
| Compound 265 | m/z＝930.4[M + H] + | Compound 526 | m/z＝938.4[M + H] + |
| Compound 301 | m/z＝849.4[M + H] + | Compound 550 | m/z＝801.4[M + H] + |
| Compound 318 | m/z＝892.4[M + H] + | Compound 388 | m/z＝836.4[M + H] + |
| Compound 377 | m/z＝852.3[M + H] + | Compound 500 | m/z＝928.4[M + H] + |
| Compound 530 | m/z＝878.4[M + H] + | Compound 546 | m/z＝847.4[M + H] + |
Preparation and evaluation of blue organic electroluminescent device
Example 1
The anode was prepared by the following procedure: the thickness of ITO is set as
Was cut into a size of 40mm × 40mm × 0.7mm, prepared into an experimental substrate having a cathode lap area, an anode, and an insulating layer pattern using a photolithography process using ultraviolet ozone and O 2 :N 2 The plasma was subjected to surface treatment to increase the work function of the anode (experimental substrate) and remove dross.
A HAT-CN layer was vacuum-deposited on an experimental substrate (anode) to a thickness of
Followed by vacuum evaporation of NPAPF on the hole injection layer to form a layer having a thickness of
A Hole Transport Layer (HTL).
Depositing a layer of alpha, beta-TNB on the hole transport layer to a thickness of
Electron Blocking Layer (EBL).
Alpha, beta-ADN is used as a host material, a compound 10 is used as a guest material (dopant), and the host material and the guest material are formed to have a thickness of 30:3
As organic electroluminescent devicesAn organic light emitting layer (EML).
Applying BP on the organic light-emitting layer 4 mPy and LiQ were simultaneously deposited at a film thickness ratio of 2:1 to form
A thick Electron Transport Layer (ETL), followed by co-evaporation of Mg: LiF at a film thickness ratio of 1:1 to form a layer having a thickness of
Then magnesium (Mg) and silver (Ag) were mixed at a rate of 1:9, and vacuum-evaporated on the electron injection layer to form an Electron Injection Layer (EIL) having a thickness of
The cathode of (2).
Further, a layer having a thickness of
Forming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device.
Wherein HAT-CN, NPAPF, alpha, beta-TNB, alpha, beta-ADN, BP 4 mPy and CP-1 have the following structural formulae:
examples 2 to 23
An organic electroluminescent device was fabricated in the same manner as in example 1, except that the compounds shown in table 8 were each used as a guest material (dopant) in place of the compound 10 in forming the organic light-emitting layer (EML).
Comparative example 1 to comparative example 4
In the comparative examples 1 to 4, an organic electroluminescent device was manufactured in the same manner as in example 1, except that the compound a, the compound B, and the compound C were respectively used as guest materials (dopants) instead of the compound 10 in forming the light emitting layer (EML).
Wherein the structural formulas of the compound A, the compound B, the compound C and the compound D are as follows:
the prepared organic electroluminescent device was subjected to performance test, and the specific test results are shown in table 7. Wherein the driving voltage, current efficiency, external quantum efficiency and color coordinate are 10mA/cm 2 Tested at a current density of (a); LT95(T95 Life) was at 20mA/cm 2 Is tested at a current density of (1).
Table 8 performance test results of organic electroluminescent device
As can be seen from the results in table 8, the organic electroluminescent devices of examples 1 to 23 significantly improved current efficiency and device lifetime while ensuring a lower driving voltage, as compared to the organic electroluminescent devices of comparative examples 1 to 4; wherein the current efficiency is improved by at least 8.5%, and the service life of the device is improved by at least 11.8%. The result shows that when the nitrogen-containing compound provided by the application is applied to an organic light-emitting layer of an organic electroluminescent device, the current efficiency and the service life of the organic electroluminescent device can be improved, and the performance of the organic electroluminescent device can be improved.
Claims (7)
1. A nitrogen-containing compound, wherein the structural formula of the nitrogen-containing compound is shown in chemical formula 1:
wherein X 1 And X 2 Are the same or different and are each independently selected from C (H) or N;
Ar 1 and Ar 2 Are identical or different and are each independently selected from substituted or unsubstituted radicals W 1 Wherein the unsubstituted radical W 1 Selected from the group consisting of:
substituted radicals W 1 Including one or more substituents independently selected from deuterium, fluoro, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, and when substituted, W 1 When the number of the substituents is 2 or more, any two substituents are the same or different;
Ar 3 selected from substituted or unsubstituted groups W 2 Wherein the unsubstituted radical W 2 Selected from the group consisting of:
substituted radicals W 2 Including one or more substituents independently selected from deuterium, fluoro, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl; when substituted W 2 When the number of the substituent(s) in (1) is 2 or more, any two of the substituents may be the same or different.
2. The nitrogen-containing compound according to claim 1, wherein the structural formula of the nitrogen-containing compound is any one of the following chemical formulas:
3. the nitrogen-containing compound according to claim 1, wherein Ar is Ar 1 And Ar 2 The same or different and each is independently selected from the group consisting of:
4. the nitrogen-containing compound according to claim 1, wherein Ar is Ar 3 Selected from the group consisting of:
5. the nitrogen-containing compound of claim 1, wherein the nitrogen-containing compound is selected from the group consisting of:
6. an organic electroluminescent device is characterized by comprising an anode and a cathode which are oppositely arranged, and a functional layer arranged between the anode and the cathode; the functional layer includes an organic light-emitting layer containing a host material and a guest material including the nitrogen-containing compound according to any one of claims 1 to 5.
7. An electronic device comprising the organic electroluminescent element according to claim 6.
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| KR102374470B1 (en) * | 2021-07-21 | 2022-03-15 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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