Patent Application
20220306655
This application claims priority to Chinese Patent Application No. CN201911416572.7, filed on Dec. 31, 2019, and Chinese Patent Application No. CN202011133615.3, filed on Oct. 21, 2020, the disclosures of which are incorporated herein by reference in their entirety as part of this application.
The present disclosure relates to the technical field of organic light-emitting materials, in particular to an organic compound, application thereof and an organic electroluminescent device.
With the development of electronic technology and the advancement of material science, the range of applications of electronic components for realizing electroluminescence or photoelectric conversion is increasingly widespread. Electronic components of this type typically each include a cathode and an anode which are oppositely disposed, and a functional layer disposed between the cathode and the anode. The functional layer consists of multiple organic or inorganic film layers and generally includes an energy conversion layer, a hole transporting layer between the energy conversion layer and the anode, and an electron transporting layer between the energy conversion layer and the cathode.
Taking an organic electroluminescent device as an example, the organic electroluminescent device generally includes an anode, a hole transporting layer, an electroluminescent layer as an energy conversion layer, an electron transporting layer, and a cathode which are stacked in sequence. When an electric voltage is applied to the anode and the cathode, the two electrodes generate an electric field, under the action of the electric field, electrons on the cathode side move towards the electroluminescent layer and holes on the anode side also move towards the light-emitting layer, electrons and holes are combined to form excitons in the electroluminescent layer, and the excitons are in an excited state to release energy outwards, thereby causing the electroluminescent layer to emit light outwards. Organic light-emitting diodes have self-luminous properties, and materials that dominate their light emission are mainly electroluminescent materials, however, current electroluminescent materials have low luminous efficacy, which often leads to failure of organic light-emitting diodes.
The present disclosure aims to increase the luminous efficacy of electroluminescent devices and prolong the service life of electroluminescent devices.
In order to achieve the above object, a first aspect of the present disclosure provides a compound having a structure as represented by the following formula (1):
wherein at least one among Q1, Q2, and Q3 is
and indicates a connective bond;
n1 and n2 are the same or different, and are respectively independently selected from 0, 1, 2, 3, or 4;
n3 and n4 are the same or different, and are respectively independently selected from 0, 1, 2, 3, 4, or 5;
n5 is selected from 0, 1, 2, or 3;
R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, a substituted or unsubstituted alkyl having 1 to10 carbon atoms, a substituted or unsubstituted aryl having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 40 carbon atoms, and a substituted or unsubstituted arylamine having 6 to 40 carbon atoms;
alternatively, two adjacent R1 and R2 are connected with each other to form a ring, or two adjacent R2 and R3 are connected with each other to form a ring, or two adjacent R3 and R4 are connected with each other to form a ring, or two adjacent R4 and R5 are connected with each other to form a ring, or two adjacent R1 and R4 are connected with each other to form a ring;
the substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, an unsubstituted alkyl having 1 to 30 carbon atoms, an unsubstituted cycloalkyl having 3 to 30 carbon atoms, an unsubstituted heterocycloalkyl having 2 to 30 carbon atoms, an aryl having 6 to 30 carbon atoms optionally substituted with an alkyl having 1 to 5 carbon atoms, an unsubstituted heteroaryl having 1 to 30 carbon atoms, an unsubstituted alkoxy having 1 to 30 carbon atoms, an unsubstituted arylamine having 6 to 30 carbon atoms, an unsubstituted alkylsilyl having 1 to 30 carbon atoms, or an unsubstituted arylsilyl having 6 to 30 carbon atoms.
A second aspect of the present disclosure provides the application of the organic compound provided by the first aspect of the present disclosure in an organic electroluminescent device.
A third aspect of the present disclosure provides an organic electroluminescent device, comprising an anode, a cathode and at least one functional layer between the anode and the cathode, where the functional layer includes a hole injecting layer, a hole transporting layer, an organic electroluminescent layer, an electron transporting layer and an electron injecting layer; the organic electroluminescent layer contains the organic compound of the first aspect of the present disclosure.
By the above technical solution, the organic compound of the present disclosure has an adamantane-six-membered ring-based structure, and the structure is combined with a solid ring centered on a boron element, which is advantageous to improve the electron stability, prevent the disappearance of excitons, promote host energy transfer, and can significantly improve the stability of carriers and improve the luminescent properties of organic light-emitting devices. And the driving voltage of the organic electroluminescent device containing the organic compound of the present disclosure can be reduced, and the open circuit voltage of the photoelectric conversion device can be increased.
Other features and advantages of the present disclosure will be described in detail in the subsequent Detailed Description.
The above and other features and advantages of the present disclosure will become more apparent by describing in detail examplary embodiments thereof with reference to the accompanying drawings.
The reference signs of main elements in the drawings are illustrated below:
100, anode; 200, cathode; 300, functional layer; 310, hole injecting layer; 320, hole transporting layer; 321, first hole transporting layer; 322, second hole transporting layer; 330, organic electroluminescent layer; 340, electron transporting layer; 350, electron injecting layer; 400, electronic device.
Exemplary embodiments will now be described more fully with reference to the accompanying drawings. Exemplary embodiments can, however, be implemented in many forms and should not be construed as limited to the embodiments set forth herein; on the contrary, these embodiments are provided so that the present disclosure will be thorough and complete, and the concept of the examplary embodiments is fully conveyed 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 provide a thorough understanding of embodiments of the present disclosure.
In the drawings, the area and layer thickness may be exaggerated for clarity. The same reference signs in the drawings denote the same or similar structures, and thus their detailed description 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 provide a thorough understanding of embodiments of the present disclosure. One skilled in the art will recognize, however, that the technical solution of the present disclosure may be practiced without one or more of the specific details, or that other methods, elements, materials, etc. may be employed. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring the principal technical creatives of the present disclosure.
The terms “the” and “said” are used to indicate the presence of one or more elements/components/etc.; the terms “including” and “having” are used in an open, inclusive sense and mean that additional elements/components/etc. may be present in addition to the listed elements/components/etc.
A first aspect of the present disclosure provides an organic compound, having a structure as represented by the following formula (1):
wherein at least one among Q1, Q2, and Q3 is
indicates a connective bond;
n1 and n2 are the same or different, and are respectively independently selected from 0, 1, 2, 3, or 4;
n3 and n4 are the same or different, and are respectively independently selected from 0, 1, 2, 3, 4, or 5;
n5 is selected from 0, 1, 2, or 3;
R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, a substituted or unsubstituted alkyl having 1 to 10 carbon atoms, a substituted or unsubstituted aryl having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 40 carbon atoms, or a substituted or unsubstituted arylamine having 6 to 40 carbon atoms;
alternatively, two adjacent R1 and R2 are connected with each other to form a ring, or two adjacent R2 and R3 are connected with each other to form a ring, or two adjacent R3 and R4 are connected with each other to form a ring, or two adjacent R4 and R5 are connected with each other to form a ring, or two adjacent R1 and R4 are connected with each other to form a ring. It should be noted that “any two adjacent R1 and R2 are connected with each other to form a ring” means that R1 and R2 may be present in a saturated or unsaturated cyclic form, or may be present independently of each other. For example, when two adjacent R1 and R2, two adjacent R2 and R3, two adjacent R3 and R4, and two adjacent R4 and R5 form rings, the ring-forming ways are , for example,
The substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, an unsubstituted alkyl having 1 to 30 carbon atoms, an unsubstituted cycloalkyl having 3 to 30 carbon atoms, an unsubstituted heterocycloalkyl having 2 to 30 carbon atoms, an aryl having 6 to 30 carbon atoms optionally substituted with an alkyl having 1 to 5 carbon atoms, an unsubstituted heteroaryl having 1 to 30 carbon atoms, an unsubstituted alkoxy having 1 to 30 carbon atoms, an unsubstituted arylamine having 6 to 30 carbon atoms, an unsubstituted alkylsilyl having 1 to 30 carbon atoms, or an unsubstituted arylsilyl having 6 to 30 carbon atoms. In the present disclosure, “the aryl having 6 to 30 carbon atoms optionally substituted with the alkyl having 1 to 5 carbon atoms” means that the aryl may be substituted with the alkyl having 1 to 5 carbon atoms, or may not be substituted with the alkyl having 1 to 5 carbon atoms.
In the present disclosure, “at least one among Q1, Q2, and Q3 is
means that one of Q1, Q2, and Q3 is
or two of Q1, Q2, and Q3 are
or three of Q1, Q2, and Q3 are
In the present disclosure, the dashed line “—” in Formula (1) indicates that a connective bond may be formed at the dashed line, or may not be formed at the dashed line. Specifically, the dashed line at Q3 indicates that Q3 may form a connective bond at this dashed line to be connected with the benzene rings to form a ring, or may not form a connective bond and not be connected with the benzene rings to form a ring; the dashed line at Q2 indicates that Q2 may form a connective bond at this dashed line to be connected with the benzene rings to form a ring, or may not form a connective bond and not be connected with the benzene rings to form a ring; the dashed line at Q1 indicates that Q1 may form a connective bond at this dashed line to be connected with the benzene rings to form a ring, or may not form a connective bond and not be connected with the benzene rings to form a ring.
In the present disclosure, when n1, n2, n3, n4, or n5 are selected from 0, the connected benzene ring is not substituted.
In the present disclosure, n1 is the number of substituent R1, and when n1 is greater than or equal to 2, any two R1 are the same or different; n2 is the number of substituent R2, when n2 is greater than or equal to 2, any two R2 are the same or different; n3 is the number of substituent R3, when n3 is greater than or equal to 2, any two R3 are the same or different; n4 is the number of substituent R4, when n4 is greater than or equal to 2, any two R4 are the same or different; n5 is the number of substituent R5, and when ns is greater than or equal to 2, any two R5 are the same or different.
In the molecular structure of the organic compound of the present disclosure, the boron element in the organic compound forms a solid ring structure with the central arylamine. And the combination of the borylamine and electron-rich spiroarylamine can improve the electron stability, prevent the disappearance of excitons, and facilitate energy transfer of the host, thus maximizing the efficiency. Linking the adamantane-six-membered ring with the solid ring centered on the boron element, due to the alkane structure of adamantane, can greatly reduce the π-π stacking effect of the molecules, and significantly improve the stability of carriers, thus improving the luminescent properties of organic light-emitting devices. The organic electroluminescent device containing the organic compound has higher luminous efficacy and longer service life.
In the present disclosure, the number of carbon atoms of R1, R2, R3, R4 and R5 refers to the number of all carbon atoms. For example, if R1, R2, R3, R4 and R5 are selected from a substituted aryl having 18 carbon atoms, the number of all carbon atoms of the aryl and the substituents thereon are 18; if R1, R2, R3, R4 and R5 are selected from a substituted alkyl having 10 carbon atoms, the number of all carbon atoms of the alkyl and the substituents thereon is 10; if R1, R2, R3, R4 and R5 are selected from a substituted heteroaryl having 10 carbon atoms, the number of all carbon atoms of the heteroaryl and the substituents thereon is 10; if R1, R2, R3, R4 and R5 are selected from a substituted arylamine having 10 carbon atoms, the number of all carbon atoms of the arylamine and the substituents thereon is 10.
In the present disclosure, the descriptions used “are each independently . . . ”, “ . . . are respectively independently” and “ . . . are independently selected from” may interchangeable, and should be understood in a broad sense, which means that specific options expressed between identical symbols in different groups do not affect each other, or means that specific options expressed between identical symbols in the same group do not affect each other. For example, ″
where each q is independently 0, 1, 2 or 3, and each R″ is independently selected from hydrogen, deuterium, fluorine, or chlorine″ means that the formula Q-1 indicates that there are q substituents R″ on the benzene ring, each R″ may be the same or different, and the options of each R″ do not affect each other; the formula Q-2 indicates that there are q substituents R″ on each benzene ring of biphenyl, the number q of R″ substituents on both benzene rings may be the same or different from each other, each R″ may be the same or different, and the options of each R″ do not affect each other.
In the present disclosure, the term “substituted or unsubstituted” means that the functional groups described after the term may have or may not have substituents (substituents are collectively referred to as Rc hereinafter for ease of description). For example, “the substituted or unsubstituted aryl” refers to an aryl with a substituent Rc or an unsubstituted aryl. The above substituent, i.e. Rc, for example, may be deuterium, halogen, cyano, a heteroaryl having 3 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, a trialkylsilyl having 3 to 12 carbon atoms, a triarylsilyl having 18 to 30 carbon atoms, an alkyl having 1 to 10 carbon atoms, a haloalkyl having 1 to 10 carbon atoms, an alkenyl having 2 to 6 carbon atoms, an alkynyl having 2 to 6 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, a heterocycloalkyl having 2 to 10 carbon atoms, a cycloalkenyl having 5 to 10 carbon atoms, a heterocycloalkenyl having 4 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, an alkamine having 1 to 10 carbon atoms, an alkylthio having 1 to 10 carbon atoms, an aryloxy having 6 to 18 carbon atoms, an arylthio having 6 to 18 carbon atoms, an alkylsulfonyl having 6 to 18 carbon atoms, a trialkylphosphino having 3 to 18 carbon atoms, or a trialkylboryl having 3 to 18 carbon atoms.
In the present disclosure, in the expression “any two adjacent substituents form a ring”, “any adjacent” may include both substituents on the same atom and one substituent on each of two adjacent atoms; when there are two substituents on the same atom, the two substituents may form a saturated or unsaturated ring (e.g., a 3- to 18-membered saturated or unsaturated ring) with the atom to which they are jointly connected; when two adjacent atoms have one substituent on each, the two substituents may be fused to a ring, e.g., a naphthalene ring, a phenanthrene ring, or an anthracene ring.
In the present disclosure, when a specific definition is not otherwise provided, “hetero” means that at least one heteroatom such as B, O, N, P, Si, Se, or S is included in one functional group and the remaining atoms are carbon and hydrogen. An unsubstituted alkyl may be a “saturated alkyl” without any double or triple bonds.
In the present disclosure, “alkyl” may include a linear alkyl or a branched alkyl. The alkyl may have 1 to 20 carbon atoms, and in the present disclosure, a numerical range such as “1 to 20” refers to each integer in the given range. For example, “1 to 20 carbon atoms” refers to an alkyl that may include 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, or 20 carbon atoms. The alkyl may also be a medium-sized alkyl having 1 to 10 carbon atoms. The alkyl may also be a lower alkyl having 1 to 6 carbon atoms. In addition, the alkyl may be substituted or unsubstituted. Specific examples of the alkyl 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, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, and the like.
In the present disclosure, the aryl refers to an optional functional or substituent derived from an aromatic hydrocarbon ring. The aryl may be a monocyclic aryl or a polycyclic aryl, in other words, the aryl may be a monocyclic aryl, a fused aryl, two or more monocyclic aryl conjugated by a carbon-carbon bond, a monocyclic aryl and a fused aryl conjugated by a carbon-carbon bond, and two or more fused aryl conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated by a carbon-carbon bond may also be considered the aryl of the present disclosure. Where the aryl does not contain heteroatoms such as B, O, N, P, Si, Se, or S. For example, in the present disclosure, phenyl, biphenyl, and the like are aryl. Examples of the aryl may include phenyl, naphthyl, fluorenyl, anthryl, phenanthryl, biphenyl, terphenyl, quaterphenyl, quinquephenyl, hexaphenyl, benzo[9,10]phenanthryl, pyrenyl, benzofluoranthenyl, chrysenyl, fluorenyl, and the like, but are not limited thereto.
In the present disclosure, the substituted aryl means that one or more hydrogen atoms of the aryl are substituted with other groups. For example, at least one hydrogen atom is substituted with deuterium atom, F, Cl, Br, I, CN, hydroxyl, amino, branched alkyl, linear alkyl, cycloalkyl, alkoxy, alkylamine, aryl, heteroaryl, or other groups. It can be understood that a substituted aryl having 18 carbon atoms means that the total number of carbon atoms of the aryl and the substituents on the aryl is 18. For example, 9,9-dimethylfluorenyl has 15 carbon atoms.
In the present disclosure, the aryl as a substituent is exemplified by, but not limited to, phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenanthryl, anthryl, 1,10-phenanthrolinyl, and the like.
In the present disclosure, the heteroaryl may be a heteroaryl including at least one of B, O, N, P, Si, Se and S as a heteroatom. The heteroaryl may be a monocyclic or polycyclic heteroaryl, that is, the heteroaryl may be a single aromatic ring system or multiple aromatic ring systems conjugated via carbon-carbon bonds, and either aromatic ring system is an aromatic monocyclic ring or an aromatic fused ring. By way of example, the heteroaryl may include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzosilyl, dibenzofuranyl, phenyl-substituted dibenzofuranyl, dibenzofuranyl-substituted phenyl, etc., but is not limited thereto. Among them, thienyl, furanyl, phenanthrolinyl, etc., are heteroaryl of the single aromatic ring system, and N-arylcarbazolyl, N-heteroarylcarbazolyl, phenyl-substituted dibenzofuranyl, dibenzofuranyl-substituted phenyl, etc., are heteroaryl of the multiple aromatic ring systems conjugated via carbon-carbon bonds. In the present disclosure, the heteroaryl may be carbazolyl, dibenzofuranyl, and the like.
In the present disclosure, the heteroaryl as a substituent is exemplified by, but not limited to, pyridyl, carbazolyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl, pyrazinyl, dibenzothienyl, dibenzofuranyl, 9,9-dimethyl-9H-9-silafluorenyl, and the like.
In the present disclosure, the arylamine is a group formed by substituting at least one hydrogen in an amine (—NH2) with an aromatic hydrocarbon. For example, an arylamine in which two hydrogens in an amine (−NH2) are substituted by benzene is a diphenylamine. Exemplarily, the arylamine may be selected from anilino, diphenylamino, benzylamino, N-methylanilino, dimethyl aniline, N-p-toluenediamine and N-m-toluenediamine, and the like. In the present disclosure, the arylamine may be selected from diphenylamino, and dinaphthylamino.
In one specific embodiment of the present disclosure, the compound has a structure as represented by the following formula (1):
wherein at least one among Q1, Q2, and Q3 is
indicates a connective bond;
n1 and n2 are the same or different, and are respectively independently 0, 1, 2, 3, or 4;
n3 and n4 are the same or different, and are respectively independently 0, 1, 2, 3, 4, or 5;
n5 is selected from 0, 1, 2, or 3;
R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, an unsubstituted alkyl having 1 to 10 carbon atoms, a substituted or unsubstituted aryl having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 40 carbon atoms, or a substituted or unsubstituted arylamine having 6 to 40 carbon atoms;
the substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, an unsubstituted alkyl having 1 to 30 carbon atoms, an unsubstituted cycloalkyl having 3 to 30 carbon atoms, an unsubstituted heterocycloalkyl having 2 to 30 carbon atoms, a substituted or unsubstituted aryl having 6 to 30 carbon atoms, an unsubstituted heteroaryl having 1 to 30 carbon atoms, an unsubstituted alkoxy having 1 to 30 carbon atoms, an unsubstituted arylamine having 6 to 30 carbon atoms, an unsubstituted alkylsilyl having 1 to 30 carbon atoms, or an unsubstituted arylsilyl having 6 to 30 carbon atoms.
In one specific embodiment of the present disclosure, R1 and R2 may be connected to form a ring, R2 and R3 may be connected to form a ring, R3 and R5 may be connected to form a ring, R1 and R4 may be connected to form a ring, and R4 and R5 may be connected to form a ring, wherein the rings are independently a fused aromatic ring or a fused heteroaromatic ring, such as xanthene ring, a fluorene ring, 10-phenyl-9,10-dihydroacridine ring, and the like. For example, in compound
R3 and R5 form a 10-phenyl-9,10-dihydroacridine ring.
In the present disclosure, the meaning of A and B “may be connected to form a ring” is that A and B are independently of each other, and the two are not connected; or is that A and B are connected with each other to form a ring. For example, R1 and R2 may be connected to form a ring, which means that R1 and R2 are independent of each other and are not connected, or Ri and R2 are connected with each other to form a ring; R2 and R3 may be connected to form a ring, which means that R2 and R3 are independent of each other and are not connected, or R2 and R3 are connected with each other to form a ring; R3 and R5 may be connected to form a ring, which means R3 and R5 are independently of each other and are not connected, or R3 and R5 are connected with each other to form a ring; R1 and R4 may be connected to form a ring, which means R1 and R4 are independent of each other and are not connected, or R1 and R4 are connected with each other to form a ring; R4 and R5 may be connected to form a ring, which means that R4 and R5 are independent of each other and are not connected, or R4 and R5 are connected to each other to form a ring.
Further, the ring formed by connecting R1 with R2 may be saturated, e.g. cyclopentane or cyclohexane, and may also be unsaturated. The ring formed by connecting R2 with R3, the ring formed by connecting R1 with R4, the ring formed by connecting R4 with R5, and the ring formed by connecting R3 with R5 are similar in meaning to the ring formed by connecting R1 with R2.
Optionally, the ring is a saturated or unsaturated 3-to 7-membered ring.
The non-positioned connective bond in the present disclosure refers to a single bond ″
extending from a ring system, which indicates that one end of the connective bond may be connected to any position in the ring system through which the bond penetrates, and the other end is connected to the remainder of the compound molecule.
For example, as shown in the formula (f) below, the naphthyl represented by the formula (f) is connected to the other positions of the molecule by two non-positioned connective bonds penetrating the bicyclic ring, which represents the meaning including any of the possible connecting modes as shown in formulas (f-1) to (f-10).
By way of further example, as shown in the formula (X′) below, the phenanthrenyl represented by the formula (X′) is connected to the other positions of the molecule by a non-positioned connective bond extending from the middle of the benzene ring on one side, which represents the meaning including any of the possible connecting modes as shown in formulas (X′-1) to (X′-4).
The non-positioned substituent in the present disclosure refers to a substituent which is connected by a single bond extending from the center of the ring system, which indicates that the substituent may be connected at any possible position in the ring system. For example, as shown in the formula (Y) below, the substituent R group represented by the formula (Y) is connected to the quinoline ring by a non-positioned connective bond, which represents the meaning including any of the possible connecting modes as shown in formulas (Y-1) to (Y-7).
In the present disclosure, the halogen may be, for example, fluorine, chlorine, bromine, or iodine.
In the present disclosure, specific examples of the trialkylsilyl include, but are not limited to, trimethylsilyl, triethylsilyl, and the like.
In the present disclosure, specific examples of the triarylsilyl include, but are not limited to, triphenylsilyl, and the like.
In the present disclosure, specific examples of the haloalkyl include, but are not limited to, trifluoromethyl.
Hereinafter, the meaning for non-positionally connected or non-positionally substituted is the same as here and will not be repeated later.
In one specific embodiment of the present disclosure, R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, fluorine, an unsubstituted alkyl having 1 to 5 carbon atoms, a substituted or unsubstituted aryl having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or a substituted or unsubstituted arylamine having 10 to 20 carbon atoms.
In one specific embodiment of the present disclosure, the substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, fluorine, an alkyl having 1 to 5 carbon atoms, a substituted or unsubstituted aryl having 6 to 20 carbon atoms, an unsubstituted heteroaryl having 3 to 20 carbon atoms, or an unsubstituted arylamine having 12 to 20 carbon atoms.
In one specific embodiment of the present disclosure, the substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium; cyan; fluorine; an alkyl having 1 to 5 carbon atoms; an aryl having 6 to 15 carbon atoms optionally substituted with methyl, ethyl, isopropyl or tert-butyl; or a heteroaryl having 5 to 12 carbon atoms.
In one specific embodiment of the present disclosure, the substituents of R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzothienyl, 9,9-dimethyl-9H-9-silafluorenyl, dibenzofuranyl, 9,9-dimethylfluorenyl, carbazolyl, or phenyl substituted with tert-butyl.
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from deuterium, cyano, halogen, an alkyl having 1 to 10 carbon atoms, or the group consisting of the following groups:
wherein
represents a chemical bond,
M1 is selected from single bond or
b1, b6, b7, b13 and b16 are the same or different, and are respectively independently 1, 2, 3, 4, or 5;
b2, b3, b4, b5, b8, b9, b11, b12, b14, b17, b18 and b19 are the same or different, and are respectively independently 1, 2, 3, or 4;
b10 is 1, 2, or 3;
b15 is 1, 2, 3, 4, 5, 6, or 7;
X is selected from O, S, Si(E20E21), C(E22E23), N(E24), or Se;
Y is selected from O, S, or N(E25);
Z1 to Z6 are the same or different, and are each independently selected from C(E′) or N, and at least one of Z1 to Z6 is N, where E′ in said Z1 to Z6 are the same or different, and are respectively independently selected from hydrogen, an alkyl having 1 to 10 carbon atoms, an aryl having 6 to 18 carbon atoms, a heteroaryl having 3 to 18 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms, or adjacent E′ may be connected to form a ring;
E1 to E25 are the same or different, and are respectively independently selected hydrogen, deuterium, halogen, cyano, an alkyl having 1 to 10 carbon atoms, an aryl having 6 to 18 carbon atoms, a heteroaryl having 3 to 18 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms, or an aryl having 6 to 18 carbon atoms substituted with alkyl; or E10 and E21 may be connected to form a ring, or E22 and E23 may be connected to form a ring, or any two E6 may be fused with the phenyl to which they are connected to form an aromatic ring, or any two E7 may be fused with phenyl to which they are connected to form an aromatic ring, where E1, E13, E14 and E19 are not aryl.
In the present disclosure, b1 is the number of substituent E1, and when b1 is greater than or equal to 2, any two E1 are the same or different; b2 is the number of substituent E2, and when b2 is greater than or equal to 2, any two E2 are the same or different; b3 is the number of substituent E3, and when b3 is greater than or equal to 2, any two E3 are the same or different; b4 is the number of substituent E4, and when b4 is greater than or equal to 2, any two E4 are the same or different; b5 is the number of substituent E5, and when b5 is greater than or equal to 2, any two E5 are the same or different; b6 is the number of substituent E6, and when b6 is greater than or equal to 2, any two E6 are the same or different; b7 is the number of substituent E7, and when b7 is greater than or equal to 2, any two E7 are the same or different; b8 is the number of substituent E8, and when b8 is greater than or equal to 2, any two E8 are the same or different; b9 is the number of substituent E9, and when b9 is greater than or equal to 2, any two E9 are the same or different; bio is the number of substituent E10, and when bio is greater than or equal to 2, any two E10 are the same or different; bii is the number of substituent E11, and when b11 is greater than or equal to 2, any two E11 are the same or different; b12 is the number of substituent E12, and when b12 is greater than or equal to 2, any two E12 are the same or different; b13 is the number of substituent E13, and when b13 is greater than or equal to 2, any two E13 are the same or different; b14 is the number of substituent E14, and when b14 is greater than or equal to 2, any two E14 are the same or different; b15 is the number of substituent Ei5, and when b15 is greater than or equal to 2, any two E15 are the same or different; b16 is the number of substituent E16, and when b16 is greater than or equal to 2, any two E16 are the same or different; b17 is the number of substituent E17, and when b17 is greater than or equal to 2, any two E17 are the same or different; b18 is the number of substituent E18, and when b18 is greater than or equal to 2, any two E18 are the same or different; b19 is the number of substituent E19, and when b19 is greater than or equal to 2, any two E19 are the same or different.
In the present disclosure, when b1 to b19 are selected from 0, the benzene ring is not substituted.
Optionally, E6 and E7 are fused with the phenyl to which they are connected to form an aromatic ring, for example, E6 and E7 are fused with the benzene ring to which they are connected to form a naphthyl.
Adjacent E′ may be connected to form a ring, which means that Z1 and Z2 form a ring, or Z2 and Z3 form a ring, or Z3 and Z4 form a ring, or Z4 and Z5 form a ring, or Z5 and Z6 form a ring, Z6 and Z1 form a ring, of course also including Z2 and Z3 form a ring and Z5 and Z6 form a ring, etc.
In the present disclosure, the meaning of A and B “may be connected to form a ring” is that A and B are independently of each other and are not connected; or A and B are connected with each other to form a ring. For instance, E20 and E21 may be connected to form a ring For example, E20 and E21 are independent of each other and are not connected, or E20 and E21 are connected with each other to form a ring. E22 and E23 may be connected to form a ring, for example, E22 and E23 are independent of each other and are not connected, or E22 and E23 are connected with each other to form a ring.
For instance, Z3 and Z4 may be connected to form a ring. For example, E′ of Z3 and E′ of Z4 are independent of each other and are not connected, or E′ of Z3 and E′ of Z4 and the atom to which E′ is connected are connected to form a ring, the ring refers to a saturated or unsaturated ring. Optionally, the number of carbon atoms of the ring may be 5, for example
or is 6, for example
and may also be 13, for example
Of course, the number of carbon atoms forming the ring may also be other values, which will not be listed one by one here, and the number of carbon atoms in the ring is not specifically defined in the present disclosure.
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from the group consisting of the following group: deuterium, cyano, fluorine, an alkyl having 1 to 5 carbon atoms, a substituted or unsubstituted aryl having 6 to 25 carbon atoms, a substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, and a substituted or unsubstituted arylamine having 12 to 20 carbon atoms, where the number of carbon atoms of the aryl in the aryl having 6 to 25 carbon atoms may be selected from 6, 8, 10, 12, 14, 16, 18, 20, or 25, and the number of carbon atoms of the heteroaryl in the heteroaryl having 3 to 20 carbon atoms may be selected from 3, 4, 5, 9, 12, 18, or 20.
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from the group consisting of deuterium, cyano, fluorine, an alkyl having 1 to 5 carbon atoms, a substituted or unsubstituted aryl having 6 to 10 carbon atoms, a substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, and a substituted or unsubstituted arylamine having 12 to 15 carbon atoms.
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from the group consisting of the following groups: deuterium, cyano, fluorine, an alkyl having 1 to 5 carbon atoms, and a substituted or unsubstituted W; and the unsubstituted W is selected from the groups below:
when W group is substituted, the sub stituents of W are selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, carbazolyl, dibenzofuranyl, dibenzothienyl, biphenyl, pyridyl, 9,9-dimethylfluorenyl, or 9,9-dimethyl-9H-9-silafluorenyl; when W has a plurality of sub stituents, the plurality of the sub stituents are the same or different.
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from the group consisting of the following groups: deuterium, cyano, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and the groups below,
In one specific embodiment of the present disclosure, said R1, R2, R3, R4, and R5 are the same or different, and are respectively independently selected from the group consisting of the following groups: deuterium, cyano, fluorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and the groups below,
In one specific embodiment of the present disclosure, the organic compound is selected from one or more of the following compounds P1 to P200:
A second aspect of the present disclosure provides application of the organic compound provided by the first aspect of the present disclosure in an organic electroluminescent device. According to the present disclosure, the organic compound can be used as an organic electroluminescent layer material of the organic electroluminescent device.
A third aspect of the present disclosure provides an organic electroluminescent device, comprising an anode, a cathode and at least one functional layer between the anode and the cathode, wherein the functional layer includes a hole injecting layer, a hole transporting layer, an organic electroluminescent layer, an electron transporting layer and an electron injecting layer; the organic electroluminescent layer comprises the organic compound provided by the first aspect of the present disclosure, optionally comprises at least one of the compounds P1 to P184.
For example, as shown in
Optionally, the compound provided by the present disclosure is used to form at least one organic film layer in the functional layer 300 to improve the life characteristics, efficiency characteristics, and reduce the driving voltage of the organic electroluminescent device. In certain embodiments, the mass production stability of the organic electroluminescent device can also be improved.
Optionally, the functional layer 300 includes an organic electroluminescent layer 330, the organic electroluminescent layer 330 contains the compound provided by the present disclosure. Where the organic electroluminescent layer 330 may be composed of the compound provided by the present disclosure, or may be composed of the compound provided by the present disclosure together with other materials.
In one embodiment of the present disclosure, as shown in
Optionally, the anode 100 includes the following anode materials, which is preferably the material having 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 oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combination of metals and oxides such as ZnO:Al or SnO2:Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but are not limited thereto. A transparent electrode containing indium tin oxide (ITO) as an anode is preferably included.
Optionally, the organic electroluminescent layer 330 consists of a single light- emitting material, or also contains a host material and a guest material. Optionally, the organic electroluminescent layer 330 consists of a host material and a guest material. Holes injected into the organic electroluminescent layer 330 and electrons injected into the organic electroluminescent layer 330 may be combined in the organic electroluminescent layer 330 to form excitons, the excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.
The guest material of the organic electroluminescent 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 particularly limited in the present disclosure. In one embodiment of the present disclosure, the guest material of the organic electroluminescent layer 330 may be Ir(piq)2(acac). In another embodiment of the present disclosure, the guest material of the organic electroluminescent layer 330 may be BD-1, or may also be the compound provided by the present disclosure.
The electron transporting layer 340 may be of a single-layer structure ,or may also be a multi-layer structure, which may include one or more electron transporting materials. The electron transporting materials may be selected from a benzimidazole derivative, an oxadiazole derivative, a quinoxaline derivative, or other electron transporting materials, which is not particularly limited in the present disclosure. For example, in one embodiment of the present disclosure, the electron transporting layer 340 may be composed of DBimiBphen and LiQ.
Optionally, the cathode 200 includes 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 multilayer materials such as LiF/Al, Liq/Al, LiO2/Al, LiF/Ca, LiF/Al and BaF2/Ca, but not limited thereto. A metal electrode containing aluminium as a cathode is preferably included.
Optionally, as shown in
Optionally, the hole transporting layer 320 includes a first hole transporting layer 321 and a second hole transporting layer 322, and the first hole transporting layer 321 is disposed to be closer to the surface of the anode 100 than the second hole transporting layer 322; and the first hole transporting layer 321 or the second hole transporting layer 322 comprises the organic compound provided by the present disclosure. Here, one of the first hole transporting layer 321 or the second hole transporting layer 322 may contain the organic compound provided by the present disclosure, or both the first hole transporting layer 321 and the second hole transporting layer 322 may contain the organic compound provided by the present disclosure. It can be understood that the first hole transporting layer 321 or the second hole transporting layer 322 may also contain other materials or may not contain other materials. It can be understood that in another embodiment of the present disclosure, the second hole transporting layer 322 may be considered as an electron blocking layer of the organic electroluminescent device.
Optionally, as shown in
The organic electroluminescent device of the present disclosure is based on the excellent properties of the organic compound of the present disclosure, has good carrier conduction efficiency and life, reduces the driving voltage of the organic electroluminescent device, and improves light-emitting properties.
The present disclosure is further illustrated below by way of examples, but the present disclosure is not limited in any way thereby.
All of the compounds of the synthetic methods not mentioned in the present disclosure are raw products obtained by commercial routes.
Analytical detection of intermediates and compounds in the present disclosure used an ICP-7700 mass spectrometer and an M5000 elemental analyzer.
Synthesis of Intermediate I-A-1
(1) 2-bromo-N-phenylaniline (50 g, 199.7 mmol) was dissolved in tetrahydrofuran THF (300 mL) to be clear, then the obtained solution was placed in a dry round-bottom flask under nitrogen protection, and was cooled to the system temperature of −78° C. with liquid nitrogen, nBuLi (2.5 M) (96.7 mL, 241.8 mmol) was started to be added dropwise while keeping the temperature constant, a solution of adamantanone (30 g, 199.7 mmol) in tetrahydrofuran THF (100 mL) was added dropwise into the system after stirring for lh, the mixture was naturally heated to room temperature after adding dropwise was finished, methanesulfonic acid (46.5 g, 483.6 mmol) was added, and the mixture was heated to reflux for lh under stirring. The reaction solution was cooled to room temperature, deionized water was added thereto to be stirred for 0.5 h, followed by extraction with ethyl acetate (200 mL), and the organic phases were mixed, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure; the resulting crude product was purified by recrystallization using ethyl acetate/ethanol (1:2) to obtain Intermediate I-A-1 (43 g, a yield of 71%) as a white solid.
Synthesis of Intermediate I-A-3
(2) Intermediate I-A-1 (5.1 g, 16.9 mmol) was added to a round-bottom flask containing xylene (50 mL), followed by addition of sodium tert-butoxide (2.3 g, 23.8 mmol), the system was heated to 180° C., followed by addition of 2,3-dichlorobromobenzene (3.8 g, 16.9 mmol) and tetra-n-butyl titanate BTP (0.08 g, 0.238 mmol), stirring was performed for 12 h, then the system was cooled to room temperature, the reaction was quenched with aqueous solution of ammonium chloride, and subjected to extraction with ethyl acetate to obtain organic phase, which was dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure; the resulting crude product was purified by silica column chromatography with dichloromethane/n-heptane (1:2) to obtain Intermediate I-A-2 (3.18 g, a yield of 42%) as a white solid and the yellow Intermediate I-A-3 (2.3 g, a yield of 19%).
Synthesis of Intermediate I-A-4
(3) Under the protection of nitrogen, Intermediate I-A-2 (2.5 g, 5.64 mmol) was dissolved in a round-bottom flask containing 50 mL toluene, and sodium tert-butoxide (1.18 g, 12.3 mmol) was added, stirring was turned on, and the system temperature was raised to 110° C., then diphenylamine (1.0 g, 6.11 mmol) and tetra-n-butyl titanate BTP (0.06 g, 0.18 mmol) were added sequentially, stirring was performed for 12 h and then the stirred product was cooled to room temperature. The reaction was quenched by the addition of aqueous solution of ammonium chloride, and subjected to extraction with ethyl acetate to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica column chromatography purification with dichloromethane/n-heptane (1:2) to obtain Intermediate I-A-4 (2.56 g, a yield of 78%) as a white solid.
Synthesis of the Organic Compound P1
(4) Under the protection of nitrogen, Intermediate I-A-4 (2.03 g, 3.52 mmol) was dissolved in a round-bottom flask containing tert-butylbenzene (20 mL), after n-butyllithium (2.5 M, 0.83 mL) was added dropwise, the mixture was heated to 200° C. and kept for 6 h, the system was cooled to room temperature, and then was cooled to −78° C. with liquid nitrogen, boron tribromide (1 M, 1.6 mL) was added slowly dropwise, after dropwise addition was finished, the reaction was reheated to 180° C., and after 2 h, the reaction mixture was quenched with aqueous solution of sodium thiosulfate, then subjected to extraction with toluene to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was recrystallized for purification with toluene to obtain the organic compound P1 (0.87 g, a yield of 44.7%) as solid. Mass spectrometry: m/z=553.3 [M+H]+.
Nuclear magnetic resonance data for the organic compound P1
1H NMR (400MHz, CD2Cl2): 8.24 (d, 1H), 7.98 (dd, 1H), 7.72-7.56 (m, 6H), 7.31 (t, 1H), 7.11-6.97 (m, 5H), 6.88-6.74 (m, 4H), 6.68 (dd, 1H), 2.35-2.13 (m, 8H), 1.91 (s, 2H), 1.73 (d, 2H), 1.56 (s, 2H).
Synthesis of the Organic Compound P12
Under the protection of nitrogen, Intermediate I-A-3 (2.3 g, 3.25 mmol) was dissolved in a round-bottom flask containing tert-butylbenzene (50 mL), after n-butyllithium (2.5 M, 1.13 mL) was added dropwise, the mixture was heated to 200° C. and kept for 6 h, the system was cooled to room temperature, and was cooled to −78° C. with liquid nitrogen, boron tribromide (1 M, 1.6 mL) was added slowly dropwise, after dropwise addition was finished, the reaction was reheated to 180° C., and after 2 h, the reaction mixture was quenched with aqueous solution of sodium thiosulfate, and then subjected to extraction with toluene to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was recrystallized for purification with toluene to obtain the organic compound P12 (1.37 g, a yield of 61.6%) as solid, Mass spectrometry: m/z=685.4 [M+H]+.
The organic compounds were prepared by the same method as in Synthesis Example 1 except that the raw material 1 in Table 1 was used instead of diphenylamine in step (3) in Example 1. Structures and characterization data of the finally prepared organic compounds are shown in Table 1.
Synthesis of Intermediate I-B
(1) p-methylaniline (4.1 g, 38.0 mmol), 9-(4-bromophenyl)-9H-carbazole (11.54 g, 35.8 mmol), tris(dibenzylideneacetone)dipalladium (0.35 g, 0.38 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.36 g, 0.76 mmol) and sodium tert-butoxide (5.48 g, 57.0 mmol) were added to toluene (80 mL) , and heated to 108° C. under nitrogen protection and stirred for 2 h; after cooling to room temperature, the reaction solution was washed with water, then dried over magnesium sulfate, and filtered, and the filtrate was decompressed to remove the solvent; the obtained crude product was purified by recrystallization wtith dichloromethane/ethyl acetate system to obtain Intermediate I-B (11.5 g, 92%) as a pale yellow solid.
Synthesis of Intermediate I-A-5
Under the protection of nitrogen, Intermediate I-A-2 (1.5 g, 3.33 mmol, prepared in Synthesis Example 1) was dissolved in a round-bottom flask containing 100 mL toluene, and sodium tert-butoxide (1.2 g, 12.7 mmol) was added, stirring was turned on, and the system temperature was raised to 150° C., followed by sequential addition of Intermediate I-B (3.25 g, 9.33 mmol) and BTP (0.1 g, 0.18 mmol), and after stirring was performed for 12 hours, the system was cooled to room temperature. The reaction was quenched by the addition of aqueous solution of ammonium chloride, and subjected to extraction with ethyl acetate to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica column chromatography purification with dichloromethane/n-heptane (1:2) to obtain Intermediate 1-A-5 (1.13 g, a yield of 44.7%) as a white solid.
Synthesis of the Organic Compound P112
(3) Under the protection of nitrogen, Intermediate I-A-5 (6.67 g, 8.8 mmol) was dissolved in a round-bottom flask containing tert-butylbenzene (20 mL), after n-butyllithium (2.5 M, 0.83 mL) was added dropwise, the mixture was heated to 200° C. and kept for 6 h, the system was cooled to room temperature, and was cooled to −78° C. with liquid nitrogen, boron tribromide (1 M, 1.6 mL) was added slowly dropwise, after dropwise addition was finished, the reaction was reheated to 180° C., and after 2 h, the reaction mixture was quenched with aqueous solution of sodium thiosulfate, and subjected to extraction with toluene to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was recrystallized for purification with toluene to obtain the organic compound P112 (0.97 g, a yield of 15%) as a solid and mass spectrometry: m/z=732.4 [M+H]+.
The organic compounds were prepared by the same method as in Example 9 except that the intermediates listed in Table 2 were synthesized by using a raw material 2 in Table 2 instead of p-methylaniline in step (1) in Example 9 and using a raw material 3 instead of 9-(4-bromophenyl)-9H-carbazole. Then by using the intermediates in Table 2 instead of the Intermediate I-B of step (2) in Example 9, the structures and characterization data of the finally prepared organic compounds are shown in Table 3.
I-C
I-D
I-E
I-F
I-G
I-H
I-I
I-J
Synthesis of Intermediates I-K
(1) After 2-bromo-N-phenylaniline (30 g, 120.9 mmol) was dissolved in 300 mL of THF under nitrogen, the system was cooled to 78° C. with liquid nitrogen, and nBuLi (241.8 mmol, 96.7 mL) was added thereto. After stirring was performed for 1 h while heat preservation, 9-fluorenone (21.8 g, 120.9 mmol) was added slowly dropwise to the system, and after stirring was performed for 12 h while heat preservation, the reaction was heated to room temperature and methanesulfonic acid (46.5 g, 483.6 mmol) was added, and the mixture was refluxed and stirred. After the reaction was carried out for 1 h, the mixture was quenched with water, subjected to extraction with ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained concentrate was purified by recrystallization with an ethyl acetate and ethanol system (1:3) to obtain Intermediate 1-K (28.05 g, a yield of 70%) as solid.
Synthesis of Intermediate I-K-1
(2) Under the protection of nitrogen, Intermediate I-A-2 (8.2 g, 18.33 mmol) was dissolved in a round-bottom flask containing 100 mL toluene, sodium tert-butoxide (3.5 g, 36.7 mmol) was added, stirring was turned on, and the system temperature was raised to 150° C., followed by sequential addition of Intermediate I-K (6.1 g, 18.33 mmol) and BTP (0.1 g, 0.18 mmol), and after stirring for 12 h, the system was cooled to room temperature. The reaction was quenched by the addition of aqueous solution of ammonium chloride, and subjected to extraction with ethyl acetate to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting was purified by silica column chromatography purification with dichloromethane/n-heptane (1:2) to obtain Intermediate I-K-1 (7.13 g, a yield of 52.5%) as a white solid.
Synthesis of the Organic Compound P170
(3) Under the protection of nitrogen, Intermediate I-K-1 (6.5 g, 8.8 mmol) was dissolved in a round-bottom flask containing tert-butylbenzene (50 mL), after n-butyllithium (2.5 M, 3.83 mL) was added dropwise, the mixture was heated to 200° C. and kept for 6 h, the system was cooled to room temperature, and was cooled to −78° C. with liquid nitrogen, boron tribromide (1 M, 9.6 mL) was added slowly dropwise, after dropwise addition was finished, the reaction was reheated to 180° C., and after 2 h, the reaction mixture was quenched with aqueous solution of sodium thiosulfate, subjected to extraction with toluene to obtain the organic phase, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting was recrystallized for purification with toluene to obtain the organic compound P170 (2.08 g, a yield of 33%) as solid. Mass spectrometry: m/z=715.72 [M+H]+.
The organic compounds were prepared by the same method as in Example 18 except that the intermediates listed in Table 4 were synthesized by using a raw material 4 in Table 4 instead of 9-fluorenone in step (1) in Example 18 and using a raw material 5 instead of 2-bromo-N-phenylaniline. Then the intermediates in Table 4 were used instead of Intermediate I-K of step (1) in Example 18. Structures and characterization data of the finally prepared compounds are shown in Table 5.
I-L
I-M
Synthesis of Intermediate II-1
(1) Magnesium ribbons (13.54 g, 564 mmol) and diethyl ether (100 mL) were placed in a dry round-bottom flask under nitrogen protection, and iodine (100 mg) was added. Then a solution of m-chlorobromobenzene (36 g, 187.0 mmol) in diethyl ether (200 mL) was slowly dropped into the flask, and after dropwise addition was finished, the mixture was heated to 35° C. and stirred for 3 h; the reaction solution was cooled to 0° C. and a solution of adamantanone (22.4 g, 149 mmol) in diethyl ether (200 mL) was slowly added dropwise into the cooled reaction solution, after dropwise addition was finished, the mixture was heated to 35° C. and stirred for 6 h; the reaction solution was cooled to room temperature, 5% hydrochloric acid was added to the cooled reaction solution until pH was smaller than 7, stirring was performed for 1 h, diethyl ether (200 mL) was added for extraction, the obtained organic phases were mixed, dried over anhydrous magnesium sulfate, and filtered, and the solvent was removed under reduced pressure; the resulting crude product was purified by silica column chromatography using n-heptane as a mobile phase to obtain Intermediate II-1 (24 g, a yield of 61%) as solid.
Synthesis of Intermediate II-2
(2) Intermediate II-1 (10.74 g, 40.9 mmol), pyridine (6.2 g, 78 mmol) and dichloromethane (150 mL) were added into a round-bottom flask, and cooled to −10° C. under nitrogen atmosphere, trifluoromethanesulfonic anhydride (11.0 g, 39 mmol) was added slowly dropwise at −10° C. to −5° C., and stirring was performed for 3 hours while heat preservation; then the reaction solution was washed with diluted hydrochloric acid until the pH was equal to 8, liquid separation was performed, the organic phase was dried over anhydrous magnesium sulfate, and filtered, and the solvent was removed under reduced pressure; the obtained crude product was purified by silica gel column chromatography with dichloromethane/n-heptane (1:2) to obtained Intermediate II-2 (14.6 g, a yield of 90.4%) as a white solid.
Synthesis of Intermediate II-3
(3) Intermediate II-2 (12.3 g, 31.17 mmol), m-chlorophenylboronic acid (3.89 g, 24.93 mmol), tetrakis(triphenylphosphine)palladium (0.72 g, 0.62 mmol), potassium carbonate (6.45 g, 46.75 mmol), tetrabutylammonium chloride (1.73 g, 6.23 mmol), toluene (80 mL), ethanol (20 mL) and deionized water (20 mL) were added into a round-bottom flask and heated to 78° C. under nitrogen protection and stirred for 6 h; the reaction solution was cooled to room temperature, toluene (100 mL) was added for extraction, the obtained organic phases were mixed, dried over anhydrous magnesium sulfate, and filtered, and the solvent was removed under reduced pressure; the resulting crude product was purified by silica column chromatography using n-heptane as a mobile phase, followed by recrystallization with a dichloromethane/ethyl acetate system to obtain Intermediate II-3 (7.5 g, a yield of 84.2%) as a white solid.
Synthesis of Intermediate II-4
(4) 2,6-dibromo-1-chlorobenzene (6.9 g, 25.5 mmol), aniline (2.4 g, 25.9 mmol), tris(dibenzylideneacetone)dipalladium (0.23 g, 0.25 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.24 g, 0.50 mmol) and sodium tert-butoxide (3.67 g, 38.22 mmol) were added into toluene (40 mL) and heated to 108° C. under nitrogen protection and stirred for 2 h; after cooling to room temperature, the reaction solution was washed with water, dried over magnesium sulfate, and filtered, and the solvent was removed from the filtrate under reduced pressure; the crude product was purified by recrystallization with a dichloromethane/ethyl acetate system to obtain Intermediate II-4 (3.2 g, a yield of 42.6%) as a pale yellow solid.
Synthesis of Intermediate II-5
(5) Intermediate II-3 (4.6 g, 12.77 mmol), Intermediate II-4 (3.8 g, 12.77 mmol), tris(dibenzylideneacetone)dipalladium (0.12 g, 0.13 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.10 g, 0.25 mmol) and sodium tert-butoxide (1.84 g, 19.17 mmol) were added to toluene (40 mL), and heated to 108° C. under nitrogen protection and stirred for 1 h; after cooling to room temperature, the reaction solution was washed with water, dried over magnesium sulfate, and filtered, and the solvent was removed from the filtrate under reduced pressure; the crude product was purified by recrystallization with toluene system to obtain Intermediate II-5 (4.35 g, a yield of 58.8%) as a white solid.
Synthesis of the Compound P182
(6) Under the protection of nitrogen, Intermediate II-5 (5.1 g, 8.8 mmol) was dissolved in a round-bottom flask containing tert-butylbenzene (50 mL), after n-butyllithium (2.5 M, 3.83 mL) was added dropwise, the mixture was heated to 200° C. and kept for 6 h, the system was cooled to room temperature, and was cooled −78° C. with liquid nitrogen, boron tribromide (1 M, 9.6 mL) was added slowly dropwise, after dropwise addition was finished, the reaction was reheated to 180° C., and after 2 h, the reaction mixture was quenched with aqueous solution of sodium thiosulfate, subjected to extraction with toluene to obtain the organic phase was, which was dried over anhydrous magnesium sulfate and filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by recrystallization with toluene to obtaind the organic compound P182 (2.07 g, a yield of 42.6%) as solid. Mass spectrometry: m/z=553.3 [M+H]+.
Preparation of an anode: a TOP substrate (manufactured by Corning) with an ITO thickness of 1500 Å was cut into a dimension of 40 mm (length)×40 mm (width)×0.7 mm (thickness), and was prepared into an experimental substrate with a cathode overlap, an anode and an insulation layer pattern by using the photoetching process, and surface treatment was performed with UV ozone and O2:N2 plasma to increase the work function of the anode (the experimental substrate) and remove scum.
m-MTDATA (4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine) was subjected to vacuum evaporation on the experimental substrate (the anode) to form a hole injecting layer (HIL) having a thickness of 100 Å, and NPB was subjected to vacuum evaporation on the hole injecting layer to form a first hole transporting layer (HTL1) having a thickness of 1000 Å.
TCTA (4,4′,4″-tris(carbazol-9-yl)triphenylamine) was subjected to evaporation on the first hole transporting layer to form a second hole transporting layer (HTL2) having a thickness of 150 Å.
α,β-ADN was used as a host, and doped with the organic compound P1 prepared by Synthesis Example 1, and the host and the dopant formed an organic electroluminescent layer (EML) having a thickness of 220 Å according to a film thickness ratio of 30:3.
DBimiBphene (4,7-Diphenyl-2,9-bi s(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,10-phenanthraline) and LiQ (8-hydroxyquinoline lithium) were mixed at a weight ratio of 1:1 and evaporated to form an electron transporting layer (ETL) having a thickness of 300 Å, metal Yb was evaporated on the electron transporting layer to form an electron injecting layer (EIL) having a thickness of 10 Å, and then magnesium (Mg) and silver (Ag) were mixed at an evaporation rate of 1:9 and were subjected to vacuum evaporation on the electron injecting layer to form a cathode having a thickness of 120 Å.
CP-1 was evaporated on the above cathode to form an organic capping layer (CPL) with a thickness of 670 Å, thereby the preparation of an organic electroluminescent device was completed.
Where the structural formulas of m-MTDATA, NPB, TCTA, α,β-ADN, DBimiBphen, CP-1, and LiQ are shown below.
The organic electroluminescent devices were prepared by employing the same method as in Device Example 1, except that the organic compound P1 in Device Example 1 was sequentially replaced by compounds other than compounds A to E listed in Table 8 to prepare the organic electroluminescent devices.
The organic electroluminescent devices were prepared by employing the same method as in Device Example 1, except that compounds A to E listed below were used instead of the organic compound 1 in Device Example 1 to prepare the organic electroluminescent devices.
The organic electroluminescent devices prepared in the Device Examples and Preparation Comparative Examples were tested for IVL (Current-Voltage-Brightness) performance of the devices under conditions of 10 mA/cm2, and T95 lifetime of the devices was tested at 15 mA/cm2. The test structures for the above tests are shown in Table 8.
It can be known From Table 8 that the performance of organic electroluminescent devices of Device Examples 1 to 21 was substantially improved compared with that of the organic electroluminescent devices of Device Comparative Examples 1 to 5, which is mainly reflected in that the operating voltage of the device is reduced by at least 8.0%, the luminous efficacy is increased by at least 8.8%, and the lifetime is increased by at least 11.03%. This is due to the adamantane-six-membered ring-based structure included in the organic compound of the present disclosure, and the structure can increase the carrier conduction efficiency and the life of organic electroluminescent devices and photoelectric conversion devices by increasing the electron density of the conjugated system throughout the organic compound and increasing the hole conduction efficiency of the organic compound. And combining a compound formed by the adamantane-six-membered ring with a solid ring centered on the boron element can greatly improve carrier stability and improve the luminescent performance of organic light-emitting devices.
Preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details in the above-described embodiments, and the technical solutions of the present disclosure may be subjected to many simple modifications within the technical idea of the present disclosure, and these simple modifications are within the protection scope of the present disclosure.
In addition, it should be noted that each specific technical feature described in the above detailed embodiments may be combined in any suitable manner without contradiction, and various possible combinations are not further described in the present disclosure in order to avoid unnecessary repetition.
In addition, any combination between the various different embodiments of the present disclosure is also possible, and should likewise be considered as the contents disclosed by the present disclosure as long as they do not depart from the idea of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201911416572.7 | Dec 2019 | CN | national |
| 202011133615.3 | Oct 2020 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2020/131873 | 11/26/2020 | WO |
