Patent Application
20230397493
This disclosure claims the priority of Chinese patent application No. CN202111367390.2, filed on Nov. 18, 2021, and Chinese patent application No. CN202111486171.6, filed on Dec. 7, 2021, the contents of which are incorporated herein by reference in their entirety as part of the disclosure.
The present disclosure belongs to the field of organic electroluminescence, and in particular provides an organic electroluminescent devices and an electronic apparatus.
In recent years, an organic electroluminescent device (OLED) has become a very popular emerging flat panel display product at home and abroad because OLED displays have the characteristics of self-luminescence, wide viewing angle, short response time, high efficiency, wide color gamut, and the like.
The organic electroluminescent device (OLED) typically includes an anode, a cathode and an organic layer disposed between the anode and the cathode. The organic layer may include a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), a hole blocking layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied to the organic electroluminescent device, holes and electrons are injected into the luminescent layer from the anode and the cathode, respectively, and the injected holes and electrons combine in the luminescent layer to form excitons in an excited state, and the excitons release energy outwards, causing the luminescent layer to emit light outwards.
Currently, there is still a problem of poor performance during use of the organic electroluminescent device, there are, for example, problems such as too high driving voltage, too low luminous efficiency, or shorter service life, which affect the field of use of the organic electroluminescent device, and thus, it is still necessary to carry out further research in this field to improve the performance of the organic electroluminescent device.
The present disclosure provides an organic electroluminescent device and an electronic apparatus to solve the problems of lower luminous efficiency and shorter service life of the organic electroluminescent device in the prior art.
In order to realize the above inventive purpose, the present disclosure adopts the following technical solution:
According to a first aspect of the present disclosure, the present disclosure provides an organic electroluminescent device, including a cathode, an anode and an organic layer;
The present disclosure aims to provide an organic electroluminescent device comprising a specific luminescent layer host material, and the luminescent layer host material comprises the first compound having strong electron properties and the second compound having relatively strong hole properties to adjust charge balance so that the organic electroluminescent device has excellent properties.
The drawings herein are incorporated into and constitute part of the description, illustrating the embodiments conforming to the present disclosure, and are used together with the description to interpret the principles of the present disclosure.
By the above drawings, specific examples of the present disclosure have been shown and will hereinafter be described in more detail. These drawings and written descriptions are not intended to limit the scope of the concept of the present disclosure in any way, but rather to illustrate the concept of the present disclosure by reference to specific embodiments for those skilled in the art.
Embodiments will now be described more comprehensively with reference to the drawings. However, the embodiments can be implemented in various forms, and should not be understood as limited to the instances set forth herein; and on the contrary, these embodiments are provided such that the present disclosure will be more comprehensive and complete, and the concepts of the embodiments are comprehensively conveyed to those skilled in the art. The described features, structures, or characteristics may be incorporated in one or more embodiments in any suitable manner. In the following description, many specific details are provided to give a sufficient understanding of the embodiments of the present disclosure.
In the drawings, for clearness, the thickness of regions and layers may be exaggerated. The same reference signs in the drawings represent the same or similar structure, so that detailed description thereof will be omitted.
The described features, structures, or characteristics may be incorporated in one or more embodiments in any suitable manner. In the following description, many specific details are provided to give a sufficient understanding of the embodiments of the present disclosure. However, those skilled in the art will realize that the technical solution of the present disclosure may be practiced without one or more of the specific details, or other methods, components, materials, etc. may be employed. In other cases, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring the primary technical ideas of the present disclosure.
The present disclosure provides an organic electroluminescent device, including a cathode, an anode and an organic layer;
In the present disclosure, at least one group A of the all group A is selected from the formula 1-A, for example, among the group A, one group A is of the formula 1-A, or two group A are selected from the formula 1-A; or three group A are selected from the formula 1-A. In the group A, when two or more group A are of the formula 1-A, each formula 1-A may be the same or different.
In the present disclosure, for
in the formula 1 (“a structure 1-B” for short), m is equal to 0, indicating that X is absent, i.e. the structure 1-B is
and when m is equal to 1, the structure 1-B is
In the present disclosure, the structure 1-B is selected from the group consisting of:
In the present disclosure, the adopted description modes “ . . . are each independently selected from”, and “ . . . are respectively and independently selected from” can be interchanged, and should be understood in a broad sense, which means that in different groups, specific options expressed between the same symbols do not influence each other, or in a same group, specific options expressed between the same symbols do not influence each other. For example, the meaning of
where each q is independently 0, 1, 2 or 3, and each R″ is independently selected from hydrogen, deuterium, fluorine and chlorine” is as follows: a formula Q-1 represents that q substituents R″ exist on a benzene ring, each R″ can be the same or different, and options of each R″ do not influence each other; and a formula Q-2 represents that each benzene ring of biphenyl has q substituents R″, the number q of the substituents R″ on the two benzene rings can be the same or different, each R″ can be the same or different, and options of each R″ do not influence each other.
In the present disclosure, the term such as “substituted or unsubstituted” means that a functional group described behind the term may have or may not have a substituent (hereinafter, the substituent is collectively referred to as Rc in order to facilitate description). For example, the “substituted or unsubstituted aryl” refers to aryl having the substituent Rc or unsubstituted aryl. The above substituent, i.e. Rc, may be, for example, deuterium, a halogen group, cyano, heteroaryl with 3 to 12 carbon atoms, aryl with 6 to 12 carbon atoms, trialkylsilyl with 3 to 12 carbon atoms, triarylsilyl with 18 to 24 carbon atoms, alkyl with 1 to 10 carbon atoms, haloalkyl with 1 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, heterocycloalkyl with 2 to 10 carbon atoms, or alkoxy with 1 to 10 carbon atoms.
In the present disclosure, a “substituted” functional group can be substituted by one or two or more substituents in the Rc; when two substituents Rc are connected to a same atom, the two substituents Rc may independently exist or may be connected to each other to form a spirocyclic ring with the atom which they are connected with jointly; and when one substituent Rc is present on each of two adjacent carbon atoms in the functional group, two adjacent substituents Rc may independently exist or may be fused with the functional group to which they are connected to form a ring.
In the present disclosure, D in the compound is deuterium.
In the present disclosure, the terms “optional” and “optionally” mean that the subsequently described event may but don't have to occur, and that the description includes instances where the event occurs or does not occur. For example, “optionally, two adjacent substituents xx form a ring”, which means that the two substituents can, but don't have to, form a ring, including scenarios in which two adjacent substituents form a ring and scenarios in which two adjacent substituents do not form a ring.
In the present disclosure, in the condition that “any two adjacent substituents form a ring”, “any two adjacent” can include the condition that a same atom has two substituents, and can also include the condition that two adjacent atoms each have one substituent; when the same atom has two substituents, the two substituents may form a saturated or unsaturated ring with the atom to which they are connected; and when two adjacent atoms each have one substituent, the two substituents may be fused to form a ring.
In the present disclosure, “optionally, in Ar4, Ar5, and Ar6, any two adjacent substituents form a ring”, which means that in Ar4, Ar8 or Ar6, any two adjacent substituents may or may not form a ring. For example, when two adjacent substituents in Ar4 form a ring, the number of carbon atoms of the ring may be 5 to 13, and the ring may be saturated or unsaturated; and the ring is, for example, cyclohexane, cyclopentane, adamantane, benzene ring, naphthalene ring, fluorene ring and the like, but is not limited thereto.
In the present disclosure, the number of carbon atoms in the substituted or unsubstituted functional group refers to the number of all carbon atoms. For example, if L is selected from substituted arylene with 12 carbon atoms, the number of all carbon atoms of the arylene and substituents on the arylene is 12. For example: if Ar1 is
then the number of carbon atoms is 7; and if L is
the number of carbon atoms is 12.
In the present disclosure, the “alkyl” may include linear alkyl or branched alkyl. The alkyl may have 1 to 10 carbon atoms, and in the present disclosure, the range of values such as “1 to 10” refers to each integer in a given range; for example, “alkyl with 1 to 10 carbon atoms” refers to alkyl that may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. In addition, the alkyl may be substituted or unsubstituted.
Optionally, the alkyl is selected from alkyl with 1 to 5 carbon atoms, and specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and pentyl.
In the present disclosure, cycloalkyl refers to saturated hydrocarbon containing an alicyclic structure, including monocyclic structure and fused structure. The cycloalkyl can have 3 to 10 carbon atoms, and the range of values such as “3 to 10” refers to each integer in a given range; for example, “cycloalkyl with 3 to 10 carbon atoms” refers to cycloalkyl that may include 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The cycloalkyl may be substituted or unsubstituted. Examples of the cycloalkyl include, for example, cyclopentyl, cyclohexyl, and adamantyl.
In the present disclosure, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl may be monocyclic aryl (e.g., phenyl) or polycyclic aryl, in other words, the aryl can be monocyclic aryl, fused aryl, two or more monocyclic aryl conjugatedly connected through carbon-carbon bonds, monocyclic aryl and fused aryl which are conjugatedly connected through a carbon-carbon bond, or two or more fused aryl conjugatedly connected through carbon-carbon bonds. That is, unless otherwise noted, two or more aromatic groups conjugatedly connected through carbon-carbon bonds can also be regarded as the aryl of the present disclosure. The fused aryl may include, for example, bicyclic fused aryl (e.g., naphthyl), tricyclic fused aryl (e.g., phenanthryl, fluorenyl, and anthryl), and the like. The aryl does not contain heteroatoms such as B, N, O, S, P, Se, Si and the like. Examples of the aryl include, but are not limited to, phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, biphenyl, terphenyl, quaterphenyl, triphenylene, pyrenyl, benzofluoranthenyl, chrysenyl, and the like.
In the present disclosure, “substituted or unsubstituted aryl” can contain 6 to 30 carbon atoms, in some embodiments, the number of carbon atoms in the substituted or unsubstituted aryl may be 6 to 25; in some embodiments, the number of carbon atoms in the substituted or unsubstituted aryl is 6 to 20; in other embodiments, the number of carbon atoms in the substituted or unsubstituted aryl is 6 to 18; and in other embodiments, the number of carbon atoms in the substituted or unsubstituted aryl is 6 to 12. For example, in the present disclosure, the number of carbon atoms in the substituted or unsubstituted aryl may be 6, 12, 13, 14, 15, 18, 20, 24, 25, 28, 29 or 30. Of course, the number of carbon atoms can also be other numbers, which will not be listed here. In the present disclosure, biphenyl can be understood as phenyl-substituted aryl or as unsubstituted aryl.
In the present disclosure, the arylene involved refers to a divalent group formed by further loss of one hydrogen atom from aryl.
In the present disclosure, the substituted aryl can be that one or two or more hydrogen atoms in the aryl are substituted by groups such as a deuterium atom, a halogen group, cyano, aryl, heteroaryl, trialkylsilyl, triarylsilyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, alkoxy, and the like. It should be understood that the number of carbon atoms in the substituted aryl refers to the total number of carbon atoms of the aryl and substituents on the aryl, for example, substituted aryl with 18 carbon atoms means that the total number of carbon atoms of the aryl and its substituents is 18.
In the present disclosure, specific examples of aryl as a substituent in L, L1, L2, each of L3, L4, L5, L6, Ar1, Ar2, Ar4, Ar5, and Ar6 include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, dimethylfluorenyl, biphenyl, and the like.
In the present disclosure, heteroaryl refers to a monovalent aromatic ring including 1, 2, 3, 4, 5, or 6 heteroatoms in the ring or a derivative thereof, and the heteroatom may be at least one of B, O, N, P, Si, Se, and S. The heteroaryl may be monocyclic heteroaryl or polycyclic heteroaryl, in other words, the heteroaryl may be a single aromatic ring system or a plurality of aromatic ring systems conjugatedly connected through carbon-carbon bonds, and any one aromatic ring system is one aromatic monocyclic ring or one aromatic fused ring. For example, the heteroaryl may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridinopyrimidyl, pyridinopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuryl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silafluorenyl, dibenzofuryl and N-arylcarbazolyl (e.g., N-phenylcarbazolyl), N-heteroarylcarbazolyl (e.g., N-pyridylcarbazolyl), N-alkylcarbazolyl (e.g., N-methylcarbazolyl), and the like, but is not limited thereto. The thienyl, furyl, phenanthrolinyl and the like are heteroaryl of the single aromatic ring system, and N-phenylcarbazolyl and N-pyridylcarbazolyl are heteroaryl of the plurality of aromatic ring systems conjugatedly connected through carbon-carbon bonds. For example, in the present disclosure, the number of carbon atoms in the substituted or unsubstituted heteroaryl can be 3, 4, 5, 6, 10, 12, 18, 20, 24, 25, 28, 29 or 30, and of course, the number of carbon atoms can also be other numbers, which will not be listed here.
In the present disclosure, the heteroarylene involved refers to a divalent group formed by further loss of one hydrogen atom from heteroaryl.
In the present disclosure, substituted heteroaryl may be that one or two or more hydrogen atoms in the heteroaryl are substituted by groups such as a deuterium atom, a halogen group, cyano, aryl, heteroaryl, trialkylsilyl, triarylsilyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, alkoxy, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl refers to the total number of carbon atoms of heteroaryl and substituents on the heteroaryl.
In the present disclosure, specific examples of heteroaryl as a substituent in each of L, L1, L2, L3, L4, L5, L6, Ar1, Ar2, Ar4, Ar8 and Ar6 include, but are not limited to, pyridyl, carbazolyl, dibenzofuranyl, and dibenzothienyl.
In the present disclosure, the halogen group may include fluorine, iodine, bromine, chlorine, and the like.
In the present disclosure, specific examples of the trialkylsilyl with 3 to 12 carbon atoms include, but are not limited to, trimethylsilyl, triethylsilyl, and the like.
In the present disclosure, specific examples of the triarylsilyl with 18 to 24 carbon atoms include, but are not limited to, triphenylsilyl.
In the present disclosure, specific examples of the haloalkyl with 1 to 10 carbon atoms include, but are not limited to, trifluoromethyl.
In the present disclosure, an unpositioned connecting bond is a single bond
extending from a ring system, which means that one end of the connecting bond can be connected with any position in the ring system through which the bond penetrates, and the other end of the connecting bond is connected with the remaining part of a compound molecule.
For example, as shown in the following formula (f), naphthyl represented by the formula (f) is connected to other positions of a molecule through two unpositioned connecting bonds penetrating a dicyclic ring, and its meaning includes any one possible connecting mode represented by formulae (f-1) to (f-10):
For example, as shown in the following formula (X′), dibenzofuranyl represented by the formula (X′) is connected with other positions of a molecule through one unpositioned connecting bond extending from the middle of a benzene ring on one side, and its meaning includes any one possible connecting mode represented by formulae (X′-1) to (X′-4):
Hereinafter, the meaning for unpositioned connection or unpositioned substitution is the same as that here, which will not be repeated later.
In some embodiments of the present disclosure, the first compound is selected from compounds represented by the following chemical formulae:
In some embodiments of the present disclosure, the first compound is selected from compounds represented by the following chemical formulae:
In some embodiments of the present disclosure, in the first compound, X1 and X2 are both C(H), and X3 is N.
In some embodiments of the present disclosure, in the first compound, X2 and X3 are both C(H), and X1 is N.
In some embodiments of the present disclosure, in the first compound, X1 and X3 are both C(H), and X2 is N.
In some embodiments of the present disclosure, in the first compound, X1 and X2 are both N, and X3 is C(H).
In some embodiments of the present disclosure, in the first compound, X1 and X3 are both N, and X2 is C(H).
In some embodiments of the present disclosure, in the first compound, X2 and X3 are both N, and X1 is C(H).
In some embodiments of the present disclosure, in the first compound, X1, X2, and X3 are all N.
In some embodiments of the present disclosure, in the first compound,
contains at least one deuterium.
In some embodiments of the present disclosure, a is selected from 1 or 2.
In some embodiments of the present disclosure, n1, n2, and n3 are all 0.
In some embodiments of the present disclosure, in the first compound, Lis selected from a single bond or phenylene.
In some embodiments of the present disclosure, in the first compound, Lis selected from a single bond or
Optionally, in the first compound, L is selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, in the first compound, each L3, L1, and L2 are each independently selected from a single bond, substituted or unsubstituted arylene with 6 to 20 carbon atoms, and substituted or unsubstituted heteroarylene with 12 to 20 carbon atoms.
Optionally, substituents in each L3, L1, and L2 are each independently selected from deuterium, a halogen group, cyano, alkyl with 1 to 5 carbon atoms, and phenyl.
Optionally, L1 and L2 are each independently selected from a single bond, substituted or unsubstituted arylene with 6 to 12 carbon atoms, and substituted or unsubstituted heteroarylene with 12 to 18 carbon atoms.
Optionally, each L3 is selected from a single bond, and substituted or unsubstituted arylene with 6 to 12 carbon atoms.
In other embodiments of the present disclosure, in the first compound, each L3, L1, and L2 are each independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzothienylene, and substituted or unsubstituted dibenzofurylene.
Optionally, substituents in each L3, the L1 and the L2 are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, and phenyl.
Optionally, L1 and L2 are each independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzothienylene, and substituted or unsubstituted dibenzofurylene.
Optionally, each L3 is independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, and substituted or unsubstituted biphenylene.
In some embodiments of the present disclosure, each L3 is independently selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, L1 and L2 are each independently selected from a single bond, and a substituted or unsubstituted group G, where the unsubstituted group G is selected from the group consisting of.
wherein, represents a chemical bond; the substituted group G contains one or more substituents each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl; and when the substituted group G contains a plurality of substituents, the substituents are the same or different.
Optionally, L1 and L2 are each independently selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, in the first compound, Ar1 and Ar2 are each independently selected from aryl with 6 to 25 carbon atoms and substituted or unsubstituted heteroaryl with 5 to 20 carbon atoms.
Optionally, substituents in the Ar1 and the Ar2 are each independently selected from deuterium, a halogen group, cyano, alkyl with 1 to 5 carbon atoms, cycloalkyl with 5 to 10 carbon atoms, aryl with 6 to 12 carbon atoms, or triarylsilyl with 18 carbon atoms.
In other embodiments of the present disclosure, in the first compound, Ar1 and Ar2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothienyl.
Optionally, substituents in the Ar1 and the Ar2 are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, triphenylsilyl, cyclohexyl, or adamantyl.
In some embodiments of the present disclosure, in the first compound, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted group G1, where the unsubstituted group G1 is selected from the group consisting of:
wherein,
represents a chemical bond; the substituted group G1 contains one or more substituents each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, triphenylsilyl, cyclohexyl or adamantyl; and when the substituted group G1 contains a plurality of substituents, the substituents are the same or different.
Optionally, Ar1 and Ar2 are each independently selected from the group consisting of:
In some embodiments of the present disclosure, the first compound is selected from the group consisting of:
In some embodiments, the second compound is selected from compounds represented by a formula 3:
In some embodiments of the present disclosure, the second compound is selected from compounds represented by the following chemical formulae:
wherein, in the formulas 2-4 to 2-6, R16 is deuterium, an n16 is selected from 1, 2, or 3.
Preferably, in the formulas 2-4 to 2-6, R16 is deuterium, and n16 is selected from 3.
In some embodiments of the present disclosure, in the second compound, L4 and L5 are each independently selected from a single bond, substituted or unsubstituted arylene with 6 to 12 carbon atoms, and substituted or unsubstituted heteroarylene with 12 to 18 carbon atoms.
Optionally, substituents in L4 and L5 are the same or different, and are each independently selected from deuterium, a halogen group, cyano, alkyl with 1 to 5 carbon atoms, or phenyl.
In other embodiments of the present disclosure, L4 and L5 are each independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzofurylene, and substituted or unsubstituted dibenzothienylene.
Optionally, substituents in L4 and L5 are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl.
In other embodiments of the present disclosure, L4 and L5 are each independently selected from a single bond, and a substituted or unsubstituted group V, where the unsubstituted group V is selected from the group consisting of:
wherein, represents a chemical bond; the substituted group V contains one or more substituents each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl; and when the substituted group V contains a plurality of substituents, the substituents are the same or different.
Optionally, L4 and L5 are each independently selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, L6 is selected from a single bond or phenylene.
In some embodiments of the present disclosure, L6 is selected from a single bond or the group consisting of:
In some embodiments of the present disclosure, Ar4 and Ar5 are each independently selected from substituted or unsubstituted aryl with 6 to 25 carbon atoms and substituted or unsubstituted heteroaryl with 12 to 20 carbon atoms.
Optionally, substituents in Ar4 and Ar5 are the same or different, and are each independently selected from deuterium, a halogen group, cyano, alkyl with 1 to 5 carbon atoms, or aryl with 6 to 12 carbon atoms.
Optionally, in Ar4 and Ar5, any two adjacent substituents form a saturated or unsaturated ring having 5 to 13 carbon atoms.
Optionally, in Ar4 and Ar5, any two adjacent substituents may form cyclohexane
cyclopentane
a benzene ring, a naphthalene ring, or a fluorene ring
Specifically, specific examples of the substituents in Ar4 and Ar5 include, but are not limited to, deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, or biphenyl.
In other embodiments of the present disclosure, Ar4 and Ar5 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, and substituted or unsubstituted dibenzothienyl.
Optionally, substituents in Ar4 and Ar5 are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl or naphthyl.
Optionally, in Ar4 and Ar5, any two adjacent substituents form a fluorene ring.
In some embodiments of the present disclosure, Ar4 and Ar5 are each independently selected from a substituted or unsubstituted group W, where the unsubstituted group W is selected from the group consisting of:
represents a chemical bond; the substituted group W contains one or more substituents each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, or naphthyl; and when the substituted group W contains a plurality of substituents, the substituents are the same or different.
Optionally, Ar4 and Ar5 are each independently selected from the group consisting of:
In some embodiments of the present disclosure, Ar6 is substituted or unsubstituted aryl with 6 to 20 carbon atoms.
Optionally, Ar6 is substituted or unsubstituted aryl with 6 to 15 carbon atoms.
Optionally, Ar6 is substituted or unsubstituted aryl with 6 to 12 carbon atoms.
Optionally, substituents in Ar6 are the same or different, and are each independently selected from deuterium, a halogen group, cyano, alkyl with 1 to 5 carbon atoms, or phenyl.
Specifically, specific examples of the substituents in Ar6 include, but are not limited to: deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl.
In other embodiments of the present disclosure, Ar6 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and substituted or unsubstituted biphenyl.
Optionally, substituents in Ar6 are the same or different, and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl.
In some embodiments of the present disclosure, Ar6 is selected from the group consisting of:
In some embodiments of the present disclosure, in the second compound, R13, R14, and R15 are all deuterium, or R6, R11, and R12 are all deuterium.
When R13, R14, and R15 are all deuterium or R6, R11, and R12 are all deuterium in the second compound described in the present disclosure, the device performance is significantly improved when the second compound is used in a host material for an organic electroluminescent device.
In some embodiments of the present disclosure, in the second compound, R6, R7, R8, R9, R10, R11, and R12 are all deuterium.
In some specific embodiments of the present disclosure, when R6, R7, R8, R9, R10, R11, and R12 in the second compound described in the present disclosure are all deuterium, the device has lower operating voltage, higher luminous efficiency, and longer service life.
Optionally, the second compound is selected from the group consisting of
The present disclosure provides an organic electroluminescent device including a cathode and an anode which are oppositely disposed, and an organic layer. The organic layer includes an organic luminescent layer, the organic luminescent layer includes a first compound and a second compound.
In some embodiments of the present disclosure, the first compound and the second compound are used as a host material for the organic luminescent layer by mixing.
In some embodiments of the present disclosure, the relative contents of the two types of compounds in the organic luminescent layer are not particularly limited in the present disclosure, and can be selected according to the specific application of the organic electroluminescent device. Generally, the mass percentage of the first compound may be 1% to 99% and the mass percentage of the second compound may be 1% to 99%, based on the total weight of the two compounds. For example, a mass ratio of the first compound to the second compound may be 1:99, 20:80, 30:70, 40:60, 45:65, 50:50, 55:45, 60:40, 70:30, 80:20, 99:1 etc.
In some embodiments of the present disclosure, the mass percentage of the first compound is 20% to 80% and the mass percentage of the second compound is 20% to 80% based on the total weight of the two compounds.
In some preferred embodiments, the mass percentage of the first compound is 30% to 60% and the mass percentage of the second compound is 40% to 70% based on the total weight of the two compounds. Preferably, the mass percentage of the first compound is 40% to 60% and the mass percentage of the second compound is 40% to 60%. More preferably, the mass percentage of the first compound is 40% to 50% and the mass percentage of the second compound is 50% to 60%.
In some embodiments of the present disclosure, the organic electroluminescent device is a phosphorescent device.
In some specific embodiments of the present disclosure, the organic electroluminescent device is a green organic electroluminescent device.
In some embodiments of the present disclosure, the organic electroluminescent device sequentially includes an anode (ITO/Ag/ITO), a hole transport layer, a hole auxiliary layer, an organic luminescent layer, an electron transport layer, an electron injection layer, a cathode (a Mg—Ag mixture), and an organic capping layer.
In one specific embodiment of the present disclosure, as shown in
Optionally, a hole blocking layer 340 may be disposed between the organic luminescent layer 330 and the electron transport layer 350. The organic luminescent layer 330 may contain organic compounds described in the first aspect of the present disclosure.
Optionally, the anode 100 includes the following anode materials which are preferably materials having a large work function that facilitate hole injection into the organic layer. Specific examples of the anode materials include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold, or an alloy thereof, metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combined metals and oxides, such as ZnO:Al or SnO2: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. In one specific embodiment of the present disclosure, ITO/Ag/ITO is selected as the anode.
Optionally, the hole transport layer 321 can include one or more hole transport materials, and the hole transport materials may be selected from a carbazole polymer, carbazole connected triarylamine compounds or other types of compounds, which are not specially limited in the present disclosure. For example, in some embodiments of the present disclosure, the hole transport layer 321 is composed of NPB.
Optionally, the hole auxiliary layer 322 may include one or more hole transport materials, and the hole transport materials may be selected from a carbazole polymer, carbazole connected triarylamine compounds or other types of compounds, which are not specially limited in the present disclosure. For example, in some embodiments of the present disclosure, the hole auxiliary layer 322 is composed of HT-7.
Optionally, the hole injection layer 310 may also be disposed between the anode 100 and the hole transport layer 321 to enhance the ability to inject holes into the first hole transport layer 321. The hole injection layer 310 can be made of a benzidine derivative, a starburst arylamine compound, a phthalocyanine derivative or other materials, which is not specially limited in the present disclosure. A material of the hole injection layer 310 may be selected from, for example, the following compounds or any combination thereof;
In one embodiment of the present disclosure, the hole injection layer 310 is composed of HAT-CN.
Optionally, the organic luminescent layer 330 may be composed of a single luminescent material, and may also include a host material and a guest material. Optionally, the organic luminescent layer 330 is composed of the host material and the guest material, holes injected into the organic luminescent layer 330 and electrons injected into the organic luminescent layer 330 can be recombined in the organic luminescent layer 330 to form excitons, the excitons transfer energy to the host material, the host material transfers energy to the guest material, and then the guest material can emit light.
The host material of the organic luminescent layer 330 can be a metal chelated compound, a distyryl derivative, an aromatic amine derivative, a dibenzofuran derivative or other types of materials, which is not specially limited in the present disclosure.
The guest material of the organic luminescent layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, which is not specially limited in the present disclosure. The guest material is also referred to as a dopant material or a dopant. The guest material can be divided into fluorescent dopants and phosphorescent dopants according to luminescence types. For example, specific examples of green phosphorescent dopants include, but are not limited to,
In one embodiment of the present disclosure, the organic electroluminescent device is a green organic electroluminescent device, the host material of the organic luminescent layer 330 is the first compound and the second compound, and the guest material is Ir(ppy)2acac.
The electron transport layer 350 can be of a single-layer structure or a multi-layer structure, and can include one or more electron transport materials, and the electron transport materials can be selected from a benzimidazole derivative, an oxadiazole derivative, a quinoxaline derivative or other electron transport materials, which are not specially limited in the present disclosure. For example, in some embodiments of the present disclosure, the electron transport layer 350 may be composed of ET-1 and LiQ. A material of the electron transport layer 350 includes, but is not limited to, the following compounds:
In one embodiment of the present disclosure, the electron transport layer 350 may be composed of ET-1 (having a structure shown above) and LiQ.
Optionally, the hole blocking layer 340 is disposed between the organic luminescent layer 330 and the electron transport layer 350. The hole blocking layer 340 may include one or more hole blocking materials, which are not particularly limited in the present disclosure.
Optionally, the cathode 200 includes the following cathode materials which are materials having a small work function that facilitate electron injection into the organic layer. Specific examples of the cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or an alloy thereof, or multilayer materials such as LiF/Al, Liq/Al, LiO2/Al, LiF/Ca, LiF/Al, and BaF2/Ca, but are not limited thereto. A metal electrode including silver and magnesium as the cathode is preferably included.
Optionally, the electron injection layer 360 may also be disposed between the cathode 200 and the electron transport layer 350 to enhance the ability to inject electrons into the electron transport layer 350. The electron injection layer 360 may include an inorganic material such as an alkali metal sulfide and an alkali metal halide, or may include a complex of an alkali metal and an organic substance. In some embodiments of the present disclosure, the electron injection layer 360 may include ytterbium (Yb).
The present disclosure also provides an electronic apparatus, including the organic electroluminescent device described in the present disclosure.
For example, as shown in
The present disclosure will be described in detail with reference to the examples, but the following description is intended to explain the present disclosure and is not intended to limit the scope of the present disclosure in any way.
Those skilled in the art will recognize that chemical reactions described in the present disclosure may be used to suitably prepare a number of organic compounds of the present disclosure, and that other methods for preparing the compounds of the present disclosure are deemed to be within the scope of the present disclosure. For example, the synthesis of those non-exemplified compounds according to the present disclosure can be successfully accomplished by those skilled in the art by modification methods such as appropriately protecting interfering groups, by utilizing other known reagents other than those described in the present disclosure, or by making some conventional modification of reaction conditions. Compounds of which synthesis methods are not mentioned in the present disclosure are all commercially available raw material products.
1,3-Dibromo-5-chlorobenzene (50.0 g, 184.9 mmol), deuterated phenylboronic acid (51.6 g, 406.8 mmol), tetrakis(triphenylphosphine)palladium (4.2 g, 3.6 mmol), potassium carbonate (76.6 g, 554.8 mmol), tetrabutylammonium bromide (1.1 g, 3.6 mmol), toluene (400 mL), ethanol (200 mL) and deionized water (100 mL) were added to a round bottom flask, and heated to 78° C. with stirring under nitrogen atmosphere, and a reaction was carried out for 18 h; the reaction mixture was cooled to room temperature, and washed with water, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product. A crude product was purified by silica gel column chromatography using n-heptane as an eluent to obtain an intermediate sub 1-A1 (39.6 g, yield: 78%) as a white solid.
(5-Chloro-biphenyl-3-yl)boronic acid (30.0 g, 129.0 mmol), deuterated bromobenzene (23.0 g, 141.9 mmol), tetrakis(triphenylphosphine)palladium (2.9 g, 2.5 mmol), potassium carbonate (53.5 g, 387.2 mmol), tetrabutylammonium bromide (0.8 g, 2.5 mmol), toluene (240 mL), ethanol (120 mL) and deionized water (60 mL) were added to a round bottom flask, and heated to 78° C. with stirring under nitrogen atmosphere, and a reaction was carried out for 16 h; the reaction mixture was cooled to room temperature, and washed with water, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product. A crude product was purified by silica gel column chromatography using n-heptane as an eluent to obtain an intermediate sub 1-A2 (21.5 g, yield: 62%) as a white solid.
2-Chloro-4-iododibenzofuran (35.0 g, 106.5 mmol), deuterated phenylboronic acid (14.8 g, 117.1 mmol), tetrakis(triphenylphosphine)palladium (2.4 g, 2.1 mmol), potassium carbonate (32.3 g, 234.3 mmol), tetrabutylammonium bromide (0.6 g, 2.1 mmol), toluene (280 mL), water (140 mL), and ethanol (70 mL) were added to a round bottom flask, and a reaction was carried out under stirring at 78° C. for 4 h under nitrogen atmosphere; after cooling to room temperature, the resulting reaction solution was subjected to extraction and liquid separation for three times by using toluene and water, an organic phase was dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as an eluent to obtain an intermediate sub 1-A3 (22.6 g, yield: 75%) as a white solid compound.
m-Chlorobenzeneboronic acid (42.4 g, 271.5 mmol), deuterated bromobenzene (40.0 g, 246.8 mmol), tetrakis(triphenylphosphine)palladium (2.8 g, 2.4 mmol), potassium carbonate (68.2 g, 493.7 mmol), tetrabutylammonium bromide (1.5 g, 4.9 mmol), toluene (320 mL), water (160 mL), and ethanol (80 mL) were added to a round bottom flask, and a reaction was carried out under stirring at 78° C. for 12 h under nitrogen atmosphere; after cooling to room temperature, the resulting reaction solution was subjected to extraction and liquid separation for three times by using toluene and water, an organic phase was dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the crude product was purified by silica gel column chromatography using n-heptane as an eluent to obtain an intermediate sub 1-I-A4 (37.2 g, yield: 78%) as white solid compound.
Sub 1-I-A4 (35.0 g, 180.7 mmol), bis(pinacolato)diboron (55.0 g, 216.8 mmol), Pd(dppf)Cl2 (1.3 g, 1.8 mmol), and KOAc (35.4 g, 361.4 mmol), were added into 1,4-dioxane (350 mL), and a reaction was carried out under reflux at 100° C. for 12 h. When the reaction was completed, extraction was performed by using dichloromethane and water. An organic layer was dried over MgSO4, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product, and the crude product was purified by silica gel column chromatography using dichloromethane and n-heptane as an eluent to obtain a white solid compound, and the white solid compound was continued to be purified by recrystallization using dichloromethane and n-heptane to obtain a compound sub 1-II-A4 (39.6 g, yield: 77%).
Sub 1-II-A4 (19.1 g, 66.9 mmol), 2-chloro-4-iododibenzofuran (20.0 g, 60.8 mmol), tetrakis(triphenylphosphine)palladium (0.7 g, 0.6 mmol), potassium carbonate (16.8 g, 121.7 mmol), tetrabutylammonium bromide (0.2 g, 0.6 mmol), toluene (160 mL), water (80 mL), and ethanol (40 mL) were added to a round bottom flask, and a reaction was carried out under stirring at 78° C. for 6 h under nitrogen atmosphere; after cooling to room temperature, the resulting reaction solution was subjected to extraction and liquid separation for three times by using toluene and water, an organic phase was dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as an eluent to obtain an intermediate sub 1-A4 (15.7 g, yield: 72%) as a white solid compound.
With reference to the synthesis method for the intermediate sub 1-A4, intermediates sub 1-AX shown in Table 1 below were synthesized by using a reactant A in Table 1 below instead of m-chlorobenzeneboronic acid and a reactant B in Table 1 below instead of 2-chloro-4-iododibenzofuran.
Sub 1-A1 (35.0 g, 127.3 mmol), indolo[2,3-A]carbazole (39.1 g, 152.8 mmol), tris(dibenzylideneacetone)dipalladium (2.3 g, 2.5 mmol), X-Phos (2.4 g, 5.0 mmol), sodium tert-butoxide (30.5 g, 318.4 mmol) and xylene (800 mL) were added to a round bottom flask, and a reaction was carried out under stirring at 140° C. for 5 h under nitrogen atmosphere nitrogen atmosphere; after cooling to room temperature, the resulting reaction solution was subjected to extraction and liquid separation for three times by using toluene and water, an organic phase was dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as an eluent to obtain a yellow solid product sub A-1 (47.2 g, yield: 75%).
With reference to the synthesis method for the intermediate sub A-1, intermediates sub A-X shown in the table below were synthesized by using the intermediate sub 1-AX in Table 2 below instead of the intermediate sub 1-A1 and a reactant C in Table 2 below instead of indolo[2,3-A]carbazole.
The intermediate sub A-1 (6.0 g, 12.1 mmol), a reactant 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine (6.2 g, 18.1 mmol), and N,N-dimethylformamide (DMIF) (90 mL) were added to a round bottom flask, the system temperature was lowered to −5° C. under nitrogen atmosphere, 6000 sodium hydride (0.6 g, 14.5 mmol) was then added, and a reaction was continued to be carried out at room temperature for 12 h; after the reaction was completed, a yellow solid was precipitated, and the product was washed well with water, and drip washed with a small amount of ethanol to take away the water to obtain a crude product; and the crude product was purified by recrystallization using dichloromethane/n-heptane to obtain a compound A38 (6.5 g, yield: 67%).
With reference to the synthesis method for the compound 38, compounds shown in Table 3 below were synthesized by using a reactant D in Table 3 below instead of the intermediate sub A-1 and a reactant E in Table 3 below instead of 2-(4-biphenyl)-4-chloro-6-phenyl-1,3,5-triazine.
Mass spectrum data for the above compounds are shown in Table 4 below.
1,3-Dichlorobenzene-D4 (30.0 g, 198.65 mmol) was added to a four-necked flask, the temperature was controlled at 25° C., fuming nitric acid (13.77 g, 218.51 mmol) and concentrated sulfuric acid (19.48 g, 198.65 mmol) were sequentially added dropwise, after adding dropwise was completed, the mixture was allowed to stand for layering, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain an intermediate K-1 (30.99 g; yield: 80%).
S-A (30 g, 146.41 mmol), S-B (18.59 g, 146.41 mmol), tetrakis(triphenylphosphine)palladium (8.45 g, 7.32 mmol), tetrabutylammonium bromide (2.36 g, 7.32 mmol), potassium carbonate (30.35 g, 219.62 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (60 mL) were added to a dry 500 mL round bottom flask which was replaced with nitrogen, and the mixture was heated to 75° C. to 80° C. under stirring for 8 h; the reaction mixture was then cooled to room temperature, deionized water (200 mL) was added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain an intermediate S-1 (9.1 g; yield: 30%).
2,4-Dichloronitrobenzene (30 g, 156.26 mmol), 2-biphenylboronic acid (34.04 g, 171.88 mmol), tetrakis(triphenylphosphine)palladium (3.6 g, 3.12 mmol), tetrabutylammonium bromide (1.00 g, 3.13 mmol), potassium carbonate (64.79 g, 468.77 mmol), toluene (240 mL), ethanol (120 mL), and deionized water (60 mL) were added to a dry 500 mL round bottom flask which was replaced with nitrogen, and the mixture was heated to 75° C. to 80° C. under stirring for 8 h; the reaction mixture was then cooled to room temperature, deionized water (200 mL) was added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane in a ratio of 1:6 as a mobile phase to obtain an intermediate A-1 (33.87 g; yield: 70%).
With reference to the synthesis method for the intermediate A-1, intermediates A-X in Table 5 below were synthesized by using a raw material 1 in Table 5 below instead of 2,4-dichloronitrobenzene and SM-X in Table 5 below instead of 2-biphenylboronic acid.
The intermediate A-1 (30 g, 96.85 mmol), triphenylphosphine (63.51 g, 242.14 mmol), and ortho-dichlorobenzene (300 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was heated to 170° C. under stirring for 18 h; the reaction mixture was then cooled to room temperature, ortho-dichlorobenzene was removed by atmospheric distillation, toluene (200 mL) was added, stirring was performed for 15 min, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain an intermediate B-1 (13.45 g; yield: 50%).
With reference to the synthesis method for the intermediate B-1, intermediates B-X in Table 6 below were synthesized by using intermediates A-X instead of the intermediate A-1.
The intermediate B-1 (15 g, 54.0 mmol), iodobenzene (16.53 g, 81.0 mmol), cuprous iodide (1.03 g, 5.4 mmol), potassium carbonate (18.63 g, 135.01 mmol), o-phenanthroline (0.54 g, 2.7 mmol), 18-crown-6 (1.43 g, 5.4 mmol), and DMIF (150 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was heated to 150° C. under stirring for 16 h; the reaction mixture was then cooled to room temperature, ethyl acetate (200 mL) and deionized water (200 mL) were added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain an intermediate C-1 (12.4 g; yield: 65%).
With reference to the synthesis method for the intermediate C-1, intermediates C-X in Table 7 below were synthesized by using intermediates B-X in Table 7 below instead of the intermediate B-1 and a raw material 2 in Table 7 below instead of iodobenzene.
The intermediate C-24 (20 g, 56.04 mmol), bis(pinacolato)diboron (21.35 g, 84.06 mmol), tris(dibenzylideneacetone)dipalladium (1.54 g, 1.68 mmol), potassium acetate (11.00 g, 112.09 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (1.60 g, 3.36 mmol), and 1,4-dioxane (200 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was heated to 100° C. under stirring for 16 h; the reaction mixture was then cooled to room temperature, ethyl acetate (200 mL) and deionized water (200 mL) were added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain CM-1 (17.6 g; yield: 70%).
With reference to the synthesis method for CM-1, an intermediate CM-2 in Table 8 below was synthesized by using an intermediate C-25 in Table 8 below instead of the intermediate C-24:
Deuterated carbazole (20 g, 114.12 mmol), N-bromosuccinimide (NBS) (50.78 g, 285.29 mmol), and DMF (200 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was stirred at room temperature for 16 h; and then ethyl acetate (200 mL) and deionized water (200 mL) were added to the reaction mixture, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain an intermediate D-1 (12.42 g; yield: 43%).
The intermediate D-1 (10 g, 39.50 mmol), iodobenzene (12.08 g, 59.25 mmol), cuprous iodide (0.75 g, 3.95 mmol), potassium carbonate (13.65 g, 98.76 mmol), o-phenanthroline (0.39 g, 1.98 mmol), 18-crown-6 (1.04 g, 3.95 mmol), and DMF (100 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was heated to 150° C. under stirring for 16 h; the reaction mixture was then cooled to room temperature, ethyl acetate (200 mL) and deionized water (200 mL) were added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain an intermediate E-1 (6.89 g; yield: 53%).
With reference to the synthesis method for the intermediate E-1, intermediates E-X in Table 9 below were synthesized by using a raw material 3 in Table 9 below instead of iodobenzene.
The intermediate E-1 (10 g, 30.37 mmol) was added to a three-necked flask containing THF (100 ml), n-butyllithium (2.07 g, 31.89 mmol) was added dropwise at −80° C., heat preservation was performed for 1 h after adding dropwise was completed, trimethyl borate (4.73 g, 45.56 mmol) was added dropwise, heat preservation was continued to be performed for 1 h, heating was performed to room temperature, and stirring was performed overnight. Hydrochloric acid (2 mol/L) was added to adjust a pH to be neutral, filtration was performed to obtain a white crude product, and the obtained crude product was pulped with n-heptane to obtain an intermediate F-1 (5.36 g, yield: 60%).
With reference to the synthesis method for the intermediate F-1, intermediates F-X in Table 10 below were synthesized by using a raw material 4 in Table 10 below instead of E-1.
The intermediate C-1 (10 g, 28.26 mmol), the intermediate F-1 (8.72 g, 29.67 mmol), palladium acetate (0.06 g, 0.28 mmol), X-Phos (0.27 g, 0.56 mmol), potassium carbonate (7.81 g, 56.52 mmol), toluene (80 mL), ethanol (40 mL), and deionized water (20 mL) were added to a dry round bottom flask which was replaced with nitrogen, and the mixture was heated to 75° C. to 80° C. under stirring for 8 h; the reaction mixture was then cooled to room temperature, deionized water (200 mL) was added, stirring was performed for 15 min, an organic phase was separated, and dried over anhydrous magnesium sulfate, filtrated, and the filtrate was concentrated in vacuum to obtain a crude product; and the obtained crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as a mobile phase to obtain a compound 221 (12.03 g; yield: 75%).
With reference to the synthesis method for the compound 221, compounds in Table 11 below were synthesized by using a raw material C in Table 11 below instead of the intermediate C-1 and a raw material F in Table 11 below instead of the intermediate F-1.
The compounds synthesized above were subjected to mass spectrometry and the data obtained are shown in Table 12 below.
NMR data of some compounds are shown in Table 13 below:
1HNMR (400 MHZ, CD2Cl2): δ7.82-7.88 (d, 2H), δ7.78-7.82
1HNMR (400 MHZ, CD2Cl2): δ7.83-7.91 (m, 3H), δ7.79-7.83
1HNMR (400 MHZ, CD2Cl2): δ8.59-8.66 (d, 1H), δ8.33-8.39
An anode was prepared by the following process: an ITO substrate of ITO (100 Å)/Ag (1000 Å)/ITO (100 Å) having a total thickness of 1200 Å was cut into a size of 40 mm (length)×40 mm (width)×0.7 mm (thickness) to be prepared into an experimental substrate with cathode, anode and insulating layer patterns by adopting a photoetching process, and surface treatment was performed by utilizing ultraviolet ozone and O2:N2 plasma to increase the work function of the anode, and the surface of the ITO substrate can be cleaned with an organic solvent to remove impurities and oil on the surface of the ITO substrate.
HAT-CN was vacuum evaporated on the experimental substrate (the anode) to form a hole injection layer (HIL) having a thickness of 100 Å, and then NPB was vacuum evaporated on the hole injection layer to form a hole transport layer having a thickness of 1120 Å.
TAPC was vacuum evaporated on the hole transport layer to form a hole auxiliary layer having a thickness of 380 Å.
Next, a compound 285 (the second compound) and a compound A6 (the first compound) were co-evaporated on the hole auxiliary layer at a mass percentage of 60%:40% as a host material for a luminescent layer, while the host material was mixed with a guest material Ir(ppy)2acac at a doping ratio of 8% to be co-evaporated to form a green luminescent layer (EML) having a thickness of 340 Å.
A compound ET-1 and LiQ were mixed in a weight ratio of 1:1 and evaporated on the luminescent layer to form an electron transport layer (ETL) having a thickness of 320 Å, Yb was evaporated on the electron transport layer to form an electron injection layer (EIL) having a thickness of 15 Å, and then magnesium (Mg) and silver (Ag) were mixed and vacuum evaporated on the electron injection layer at an evaporation rate of 1:9 to form a cathode having a thickness of 120 Å.
In addition, CP-1 having a thickness of 600 Å was vacuum evaporated on the above cathode, thereby completing the manufacture of the green organic electroluminescent device.
An organic electroluminescent device was manufactured by the same method as that in Example 1 except that a compound combination in Table 14 was used instead of the luminescent layer host compound combination in Example 1 when the luminescent layer was manufactured.
An organic electroluminescent device was manufactured by the same method as that in Example 1 except that a compound combination in Table 15 was used instead of the luminescent layer host compound combination in Example 1 when the luminescent layer was manufactured.
When the organic electroluminescent device was manufactured, the structures of materials used in the comparative examples and the examples are as follows.
The green organic electroluminescent devices manufactured in Examples 1 to 56 and Comparative examples 1 to 4 were subjected to performance test, specifically the current-voltage-brightness (IVL) performance of the devices was tested under the condition of 10 mA/cm2, and the T95 device service life was tested under the condition of 20 mA/cm2, and the test results are shown in Table 14 below.
It can be seen from the results in Table 14 that the examples of the present disclosure have the advantages that the current efficiency (Cd/A) was improved by at least 16.200 and the service life was improved by at least 22.8% compared with Comparative examples 1 to 4.
It can be seen from the above results that the present disclosure provides an organic electroluminescent device adopting a specific luminescent layer host material combination, and the device performance was significantly improved compared with Comparative examples 1 to 4.
An organic electroluminescent device was manufactured by the same method as that in Example 1 except that a luminescent layer host compound mixing ratio (mass percent) in Table 15 was used instead of the luminescent layer host compound mixing ratio in Example 1 when the luminescent layer was manufactured.
An organic electroluminescent device was manufactured by the same method as that in Example 2 except that a luminescent layer host compound mixing ratio (mass percent) in Table 15 was used instead of the luminescent layer host compound mixing ratio in Example 2 when the luminescent layer was manufactured.
Referring to Table 15 above, compared with Examples 1 and 2, the performance of the devices was also changed when the luminescent layer host compound mixing ratio was different in Examples 57-60. Specifically, the current efficiency was improved by at least 7.500 in Example 1 compared with Examples 57 and 58, and similarly, the current efficiency was improved by at least 8.800 in Example 2 compared with Examples 59 and 60. Therefore, when the mass ratio of the second compound to the first compound in the present disclosure is 600%:40%, the device performance is optimal.
The organic electroluminescent device of the present disclosure is composed of the first compound having strong electron properties and the second compound having relatively strong hole properties to adjust charge balance so that the organic electroluminescent device has excellent properties. According to the second compound for the organic electroluminescent device, specific 3,3-bicarbazole is used as a parent core, deuteration is performed in at least two ortho positions of a connecting bond of bicarbazole, and aryl is connected to one carbazole ring, and an electron donating group is connected to biscarbazole, and such a specific combination reduces the twist angle between two carbazole rings, and improves the conjugation, thereby improving the hole mobility and charge transport balance of a host material.
Second, the simultaneous introduction of deuterated groups on both types of materials used in the present disclosure can reduce the molecular volume of the compounds, reduce the molecular spacing between the two compounds, improve the carrier transport efficiency, and thus significantly improve the stacking characteristics and chemical stability of the materials; and using the above two materials as a mixed host material for the green organic electroluminescent device can reduce the operating voltage of the organic electroluminescent device and improve the luminous efficiency as well as the service life of the device.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111367390.2 | Nov 2021 | CN | national |
| 202111486171.6 | Dec 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/076245 | 2/14/2022 | WO |
