Fluorenyl triazine compound containing deuterated benzene ring, organic electronic material, organic electroluminescent device and application

Abstract

The invention relates to a fluorenyl triazine compound containing a deuterated benzene ring, an organic electronic material, an organic electroluminescent device and application. The fluorenyl triazine compound containing the deuterated benzene ring has a structure as shown in a formula I; wherein at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1 and Ar2 is a deuterated benzene ring; and L1 represents a single bond, a phenylene group or a deuterated phenylene group. The fluorenyl triazine compound containing the deuterated benzene ring can be used as an organic electronic material for preparing an organic electroluminescent device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be prolonged. # imgabs0 #

Description

Technical Field

[0001] The present application relates to the technical field of organic electroluminescence, and particularly relates to a fluorene-based triazine compound containing a deuterated benzene ring, an organic electronic material, an organic electroluminescent device, and applications thereof. Background Art

[0002] The working principle of organic electroluminescent devices (OLEDs) is as follows: holes and electrons injected through electrodes recombine in the light-emitting layer to form excitons, and the excitons undergo radiative transitions to generate light emission. OLEDs have the advantages of active light emission, short response time, high color contrast, low energy consumption, etc., and thus are widely used in fields such as mobile phones, flat panel displays, televisions, lighting, and vehicle-mounted displays. In 1963, the electroluminescence phenomenon of single crystal anthracene of organic compounds was first discovered. In 1987, an OLED device was reported that used a diaryl diamine as a hole transport material (HTM) and tris(8-hydroxyquinoline) aluminum (Alq3) as a light-emitting material and an electron transport material, and its maximum brightness reached 1000 cd / m 2 , and since then, OLEDs have developed rapidly, and have gradually replaced liquid crystal display panels to become the main force of the new generation of flat panel displays, and also have great potential in flexible displays.

[0003] In recent years, organic electroluminescent devices have been gradually improved. However, in order to further meet the increasing requirements for the optoelectronic performance of OLED devices, it is still necessary to develop materials that are more excellent in terms of improving the light-emitting efficiency and lifespan of the devices. Summary of the Invention

[0004] Based on this, it is necessary to provide a fluorene-based triazine compound containing a deuterated benzene ring, an organic electronic material, an organic electroluminescent device, and applications thereof. The fluorene-based triazine compound containing a deuterated benzene ring can be used as an organic electronic material for preparing an organic electroluminescent device, which can effectively improve the light-emitting efficiency of the device and extend the service life of the device.

[0005] In the first aspect of the present application, there is provided a fluorene-based triazine compound containing a deuterated benzene ring, which has the structure shown in Formula I:

[0006]

[0007] In Formula I, at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1, and Ar2 is a deuterated benzene ring, and L1 is a single bond, a phenylene group, or a deuterated phenylene group.

[0008] In some embodiments, in Formula I, R1, R2, R3, R4, R5, R6 and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group or a deuterated phenyl group; L1 is a single bond, a phenylene group or a deuterated phenylene group; L2 is a single bond, a phenylene group or a substituted phenylene group; Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, and any one of a C3-C 30 substituted heteroaryl group;

[0009] wherein at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1 and Ar2 is a deuterated benzene ring.

[0010] In some embodiments, in Formula I, R1, R2, R3, R4, R5, R6 and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group or a deuterated phenyl group;

[0011] L1 is a single bond, a phenylene group or a deuterated phenylene group;

[0012] L2 is a single bond, a phenylene group or a substituted phenylene group, wherein the phenylene group in the substituted phenylene group is substituted by 1, 2, 3 or 4 groups selected from the group consisting of a methyl group, a bromo group, a chloro group and a deuterium atom;

[0013] Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, and any one of a C3-C 30 substituted heteroaryl group; wherein the aryl group in the C6-C 30 substituted aryl group and the heteroaryl group in the C3-C 30 substituted heteroaryl group are each independently substituted by one or more groups selected from the group consisting of a deuterium atom, a cyano group, a substituted phenyl group and a pyridyl group, and the phenyl group in the substituted phenyl group is substituted by 1 or more cyano groups;

[0014] wherein at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1 and Ar2 is a deuterated benzene ring.

[0015] In some embodiments, in Formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group. At this time, the fluorene-based triazine compound containing a benzene ring can also be denoted as "a compound containing deuterated phenyl fluorene and a triazine group".

[0016] In some embodiments, in Formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group; L1 is a single bond or a phenylene group.

[0017] In some embodiments, in Formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group; L1 is a single bond or a phenylene group; L2 is a single bond, a phenylene group or a substituted phenylene group; Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, and any one of a C3-C 30 substituted heteroaryl group.

[0018] In some embodiments, L2 is a single bond, or L2 is a phenylene group or a deuterated phenylene group.

[0019] In some embodiments, L2 is a single bond.

[0020] In some embodiments, L2 is a phenylene group or a deuterated phenylene group.

[0021] In some embodiments, L2 is a single bond, or L2 is a phenylene group or a deuterated phenylene group; when L2 is a phenylene group or a deuterated phenylene group, the number of deuterium atoms in the deuterated phenylene group is 1, 2, 3 or 4; the two connecting sites of L2 are ortho, meta or para positions.

[0022] In some embodiments, L2 is a phenylene group or a deuterated phenylene group, the number of deuterium atoms in the deuterated phenylene group is 1, 2, 3 or 4; the two connecting sites of L2 are ortho, meta or para positions.

[0023] In some embodiments, the fluorene-based triazine compound containing a deuterated benzene ring is a compound containing a deuterated phenyl fluorene and a triazine group, and the compound containing a deuterated phenyl fluorene and a triazine group has the structure shown in Formula I;

[0024] In Formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group;

[0025] L1 is a single bond or a phenylene group;

[0026] L2 is a single bond, a phenylene group or a substituted phenylene group, wherein the phenylene group in the substituted phenylene group is substituted by 1, 2, 3 or 4 groups selected from the following group: a methyl group, a bromo group, a chloro group and a deuterium atom;

[0027] Ar1 and Ar2 are each independently a C6-C 30 aryl, C6-C 30 substituted aryl, C3-C 30 heteroaryl, or C3-C 30 substituted heteroaryl; wherein, the aryl in the C6-C 30 substituted aryl and the heteroaryl in the C3-C 30 substituted heteroaryl are each independently substituted by one or more groups selected from the group consisting of a deuterium atom, a cyano group, a substituted phenyl group, and a pyridyl group, and the phenyl in the substituted phenyl group is substituted by one or more cyano groups.

[0028] In a second aspect of the present application, there is provided an organic electronic material containing the fluorene-based triazine compound containing a deuterated benzene ring described in the first aspect of the present application (which may be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group).

[0029] In a third aspect of the present application, there is provided an organic electroluminescent device, which at least includes an anode, a cathode, and an organic layer; the organic layer includes at least one structural layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer;

[0030] wherein, at least one structural layer in the organic layer contains the fluorene-based triazine compound containing a deuterated benzene ring described in the first aspect of the present application (which may be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) and at least one of the organic electronic materials described in the second aspect of the present application.

[0031] In some embodiments, the organic layer includes at least one structural layer selected from the hole blocking layer and the electron transport layer; wherein, at least one structural layer in the hole blocking layer and the electron transport layer contains the fluorene-based triazine compound containing a deuterated benzene ring described above (which may be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) and at least one of the organic electronic materials described above.

[0032] In some embodiments, the organic electroluminescent device includes the electron transport layer, and the electron transport layer contains the fluorene-based triazine compound containing a deuterated benzene ring described above (which may be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) and at least one of the organic electronic materials described above.

[0033] In a fourth aspect of the present application, there is provided the use of the fluorene-based triazine compound containing a deuterated benzene ring described in the first aspect of the present application (which may be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) or the organic electronic material described in the second aspect of the present application, at least including the use in the preparation of an organic electroluminescent device.

[0034] The present application provides a fluorene-based triazine compound containing a deuterated benzene ring (which can be denoted as the compound of formula I). Its structure contains a fluorene group and a triazine group simultaneously, and contains a deuterated benzene ring. The deuterated benzene ring in the compound of formula I may include at least one of a deuterated phenyl group and a deuterated phenylene group. Among them, fluorene has good optoelectronic properties and thermal stability, can effectively enhance the thermal stability of the material, can increase the glass transition temperature of the compound (such as increasing the glass transition temperature to greater than 110 °C), which is beneficial to improving the device lifetime. The triazine group has a strong electronegativity and a high electron mobility, and can effectively improve electron transport and electron injection. By introducing a deuterated benzene ring, the device prepared with this compound can reduce the vibrational energy loss of the compound, improve the exciton-to-photon conversion efficiency, enhance the light-emitting efficiency of the device and extend the device lifetime. When the fluorene-based triazine compound containing a deuterated benzene ring is used as an organic layer of an organic electroluminescent device, based on the synergistic effect of each group in the overall structure of the compound, it can effectively improve the light-emitting efficiency of the device and extend the service life of the device.

[0035] The present application also provides a compound containing a deuterated phenyl fluorene and a triazine group. Its structure contains a fluorene group and a triazine group simultaneously, and a deuterated phenyl group is connected to the fluorene group. Among them, fluorene has good optoelectronic properties and thermal stability, can effectively enhance the thermal stability of the material, can increase the glass transition temperature of the compound (such as increasing the glass transition temperature to greater than 110 °C), which is beneficial to improving the device lifetime. The triazine group has a strong electronegativity and a high electron mobility, and can effectively improve electron transport and electron injection. By introducing a deuterated phenyl group on the fluorene group, the device prepared with this compound can reduce the vibrational energy loss of the compound, improve the exciton-to-photon conversion efficiency, enhance the light-emitting efficiency of the device and extend the device lifetime. When the compound containing a deuterated phenyl fluorene and a triazine group is used as an organic layer of an organic electroluminescent device, based on the synergistic effect of each group in the overall structure of the compound, it can effectively improve the light-emitting efficiency of the device and extend the service life of the device.

[0036] When the fluorene-based triazine compound containing a deuterated benzene ring (which can be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) is used as at least one of an electron transport material and a hole blocking material of an organic electroluminescent device, it is more conducive to preparing a device with high efficiency and long lifetime. In addition, it is also conducive to reducing the driving voltage.

[0037] When using a fluorene - based triazine compound containing a deuterated benzene ring (which can be, but is not limited to, the aforementioned compound containing a deuterated phenyl fluorene and a triazine group) as an electron - transporting material in an organic electroluminescent device, it is beneficial for intermolecular stacking during film preparation, improves charge transfer, increases the charge - transporting ability of the material, and can reduce the operating voltage of the electronic device, thereby obtaining a device with a low driving voltage, high luminous efficiency, and long device life. Brief Description of the Drawings

[0038] To more clearly illustrate the technical solutions in the embodiments and implementations of the present application and to more fully understand the present application and its beneficial effects, the following will briefly introduce the drawings required for the description of the embodiments or implementations. Obviously, the following - described drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings. It should also be noted that the drawings are all drawn in a simplified form and are only used to conveniently and clearly assist in explaining the present application. The various dimensions of each component shown in the drawings are arbitrarily shown, which may be accurate or may not be drawn to actual scale. For example, to make the illustration clearer, the dimensions of some components in the drawings are appropriately exaggerated. Unless otherwise specified, the components in the drawings are not drawn to scale. The various drawings of the present application do not limit each dimension of each component.

[0039] Among them, the same reference numerals represent the same parts in the following description.

[0040] Figure 1 It is a schematic structural diagram of an organic electroluminescent device in an embodiment of the present application.

[0041] Figure 2 The schematic structural diagram of an organic electroluminescent device in an embodiment of the present application corresponds to a single - electron device structure.

[0042] Description of Reference Numerals: 110 is a glass substrate, 120 is an anode, 130 is a hole - injection layer, 140 is a hole - transporting layer, 150 is a blocking layer, 160 is a light - emitting layer, 170 is a hole - blocking layer, 180 is an electron - transporting layer, 190 is an electron - injection layer, and 200 is a cathode. Detailed Embodiments

[0043] The present application will be further described in detail below in conjunction with the accompanying drawings, embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and not to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of the disclosed content of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without departing from the connotation of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner with another embodiment to produce a new embodiment. In addition, in the following description, a large number of details are given to provide a more thorough understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs. The terms used in the description of the present application in this specification are only for the purpose of describing the embodiments and examples and are not intended to limit the present application.

[0045] In this application, the terms "a plurality of", "a variety of", "multiple times", "a number of", "several", etc., unless otherwise specified, mean greater than or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.

[0046] In this application, unless otherwise stated, "one or more" means any one of the listed items or any combination of the listed items. Similarly, in other cases where "one or more" and other expressions indicate "one or more", unless otherwise stated, the same understanding is made.

[0047] In this application, the "suitable combination method", "suitable method", "any suitable method", etc., the "suitable" is subject to being able to implement the technical solution of this application, solve the technical problems of this application, and achieve the expected technical effects of this application.

[0048] In this application, "preferred", "better", "more preferably", "should be", "relatively better", "more preferably" are only used to describe embodiments or examples with better effects. It should be understood that they do not constitute a limitation on the protection scope of this application. If "preferred" appears in multiple places in a technical solution, unless otherwise specified and there are no contradictions or mutual restrictions, each "preferred" is independent of each other.

[0049] In this application, terms such as "further", "even further", "specially", "for example", "such as", "example", "exemplification", etc. are used for descriptive purposes, indicating an association in terms of the covered content between different technical solutions before and after. However, they should not be construed as a limitation on the previous technical solution, nor as a limitation on the protection scope of this application. In this application, unless otherwise specified, A (such as B) means that B is a non-restrictive example of A, and it can be understood that A is not limited to B.

[0050] In this application, "optionally", "optional", "option" mean that it can be either present or absent, that is, it refers to any one of two alternative schemes of "present" or "absent". If there are multiple "options" in a technical solution, unless otherwise specified and there are no contradictions or mutual restrictions, each "option" is independent.

[0051] The terms "comprising", "including", and "containing" used in this application are synonyms, which are inclusive or open-ended, and do not exclude additional, unrecited members or features. Members or features include, for example, materials or components, structures, elements, instruments, etc.; non-restrictive examples of members or features also include actions, conditions for actions to occur, timing, states, etc.

[0052] In this application, in a technical feature or technical solution described in an open language, it includes a closed technical feature or technical solution composed of the listed content, and also includes an open technical feature or technical solution containing the listed content.

[0053] In this application, for units related to data ranges, if there is only a unit after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3~5h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours), and it has the same meaning as 3h~5h. In addition, the above understanding method also applies to similar descriptions of other parameters such as temperature and size.

[0054] In this application, for a method process involving multiple steps, unless there are clear different descriptions in this article, the execution of these steps has no strict order limitation, and it can be executed in other orders than the described one. Moreover, any one step can include multiple sub-steps or multiple stages. These sub-steps or stages do not necessarily need to be executed at the same moment, but can be executed at different moments, and their execution order does not necessarily need to be sequential, but can be executed alternately or simultaneously with other steps or a part of the sub-steps or stages of other steps.

[0055] In this application, for exemplary descriptions such as "in some embodiments" or "in one embodiment", etc., it can cover but is not limited to the following meaning: These solutions can be combined with other solutions in a suitable manner to form a new technical solution.

[0056] In this application, in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are only for descriptive purposes and cannot be construed as indicating or implying relative importance or quantity, nor can they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumerative description and should be understood not to constitute a closed limitation on quantity.

[0057] In this application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values within this numerical interval is considered continuous and includes the two numerical endpoints of this numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within this numerical interval, it includes the two endpoint integers of this numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad inclusion of numerical interval types such as a percentage interval, a ratio interval, a ratio value interval, etc.

[0058] In this application, unless otherwise stated, the term "hydrocarbon compound" refers to a compound composed of carbon atoms and hydrogen atoms. The "aromatic ring hydrocarbon compound" refers to a hydrocarbon compound containing an aromatic ring.

[0059] In this application, unless otherwise stated, the term "group" refers to an atom or atomic group having at least one covalent bond connection site, and can be a monovalent group, a divalent group or a polyvalent group. In this application, unless otherwise specified, the groups involved refer to monovalent groups. As non-limiting examples, monovalent groups such as a chloro group (Cl-), a methyl group (-CH3), etc., and divalent groups such as a divalent phenyl group or a phenylene group (-Ph-, where Ph refers to a benzene ring and the chemical formula of Ph is C6H4), etc. The covalent bond connection site can be a single bond connection site or an unsaturated bond connection site (such as CH2=), and unless otherwise specified, it refers to a single bond connection site.

[0060] In this application, unless otherwise stated, the term "aryl" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring hydrocarbon compound, that is, a monovalent connection site is directly formed on the ring, and it can be a monocyclic aryl group, or a fused-ring aryl group, or a polycyclic aryl group. For a polycyclic ring species, at least one is an aromatic ring system. For example, "C6-C 10"Aryl" refers to an aryl group containing 6 to 10 carbon atoms, and each occurrence can independently be a C6 aryl group, a C8 aryl group, a C9 aryl group or a C 10 aryl group. Also, for example, "C6-C 20 aryl" refers to an aryl group containing 6 to 20 carbon atoms, and each occurrence can independently be, but is not limited to, a C6 aryl group (such as a phenyl group), a C6 aryl group (such as a benzocyclobutenyl group), a C8 aryl group (such as a phenylcyclobutenyl group), a C9 aryl group (such as an indenyl group), a C 10 aryl group (such as a naphthyl group), a C 12 aryl group (such as an acenaphthylenyl group, a biphenyl group), a C 13 aryl group (such as a fluorenyl group), a C 14 aryl group (such as an anthracenyl group, a phenanthrenyl group), a C 18 aryl group (such as a triphenylenyl group) or a C 20 aryl group (such as a binaphthylenyl group). Examples of suitable aromatic hydrocarbon compounds include, but are not limited to: benzene, phenylcyclobutene, biphenyl, indene, naphthalene, acenaphthylene, fluorene, anthracene, phenanthrene, triphenylene, binaphthylene and their derivatives.

[0061] In this application, unless otherwise specified, the term "heteroaryl" refers to an aromatic heterocyclic group, which can be a monovalent group formed by replacing at least one carbon atom in an aryl group with a non-carbon atom, or a monovalent group formed by replacing at least one carbon atom in a cyclopentadienyl group with a non-carbon atom. The non-carbon atoms can be, but are not limited to, N atoms, O atoms, S atoms, etc. For example, "C3-C 10 heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms, and each occurrence can independently be a C3 heteroaryl group (such as an imidazolyl group, etc.), a C4 heteroaryl group (such as a furyl group, etc.), a C5 heteroaryl group (such as a pyridyl group, etc.), a C6 heteroaryl group, a C7 heteroaryl group (such as a benzimidazolyl group, etc.), a C8 heteroaryl group (such as an indolyl group, etc.), a C9 heteroaryl group (such as a quinolinyl group, etc.) or a C 10 heteroaryl group (such as a pyrrolodipyridyl group). Also, for example, "C3-C 20 heteroaryl" refers to a heteroaryl group containing 3 to 20 carbon atoms, and each occurrence can independently be, but is not limited to, a C3 heteroaryl group, a C4 heteroaryl group, a C5 heteroaryl group, a C6 heteroaryl group, a C8 heteroaryl group, a C9 heteroaryl group, a C 10 heteroaryl group, a C 12 heteroaryl group, a C 13 heteroaryl group, a C 14 heteroaryl group, a C 18 heteroaryl group or a C 20Heteroaryl. Suitable examples include, but are not limited to, heteroaryls derived from the following heteroaromatic rings (the number of carbon atoms is marked in subscript in parentheses): furan (C4), benzofuran (C8), thiophene (C4), benzothiophene (C8), pyrrole (C4), pyrazole (C3), imidazole (C3), oxazole (C3), thiazole (C3), indole (C8), carbazole (C 12 ), pyrroloimidazole (C5), pyrrolopyrrole (C6), thiophenopyrrole (C6), thiophenothiophene (C6), furanopyrrole (C6), furanofuran (C6), thiophenofuran (C6), thiophenopyridine (C7), furanopyridine (C7), benzoxazole (C7), benzisoxazole (C7), benzothiazole (C7), benzisothiazole (C7), benzimidazole (C7), pyridine (C5), pyrazine (C4), pyridazine (C4), pyrimidine (C4), triazine (C3), quinoline (C9), isoquinoline (C9), naphthyridine (C8, such as phthalazine), quinoxaline (C8), phenanthridine (C 13 ), peridine (C 11 ), quinazoline (C8) and quinazolinone (C8).

[0062] In this application, unless otherwise specified, for a "substituted group", the number of carbon atoms contained in the group can also be marked in a similar manner. Depending on the position of the carbon atom number marking symbol, it can only limit the number of carbon atoms in the unsubstituted form, or limit the total number of carbon atoms in the substituted form. For example, "substituted C6-C 30 aryl" means that the total number of carbon atoms in the aryl itself is 6-30, but the number of carbon atoms in the substituents on the aryl is not particularly limited, while "C6-C 30 substituted aryl" means that the total number of carbon atoms in the aryl and the substituents on the aryl is 6-30.

[0063] In this application, for the site where a covalent bond is drawn from any suitable position on the ring, taking the example of drawing a single bond from a benzene ring, it can be represented in the way, indicating the covalent bond connection site. "Any suitable position on the ring" refers to the position where it is allowed to be a covalent bond connection site. For example, for an aromatic ring, it corresponds to the position where no other substituents are provided. For example, any one of the six carbon atoms can be used as a single bond connection site, any one of the three carbon atoms can be used as a single bond connection site, (pyridyl) any one of the five carbon atoms can be used as a single bond connection site. The cyclic group represented in the above manner means that there is no particular limitation on the position where the covalent bond is drawn. Taking pyridyl as an example, it can be (ortho), (meta) or (para-position).

[0064] In the present application, unless otherwise specified, the term "deuterated benzene ring" refers to a substituted benzene ring structure formed by replacing at least one hydrogen (H) atom on the benzene ring with a deuterium (D) atom. The deuterated benzene ring used herein can be a monovalent deuterated phenyl group or a divalent deuterated phenylene group.

[0065] In the present application, unless otherwise specified, the term "deuterated phenyl group" refers to a substituted phenyl group formed by replacing at least one hydrogen (H) atom in the phenyl group with a deuterium (D) atom. Without special specification, the number and position of deuterium atoms can be arbitrary. The number of deuterium atoms can be 1, 2, 3, 4, or 5. The two ortho-positions, two meta-positions, and para-position on the phenyl group can all be deuterated or not deuterated, as long as at least one of the positions is deuterated.

[0066] In the present application, the number of deuterium atoms in the deuterated phenyl group can also be represented by the "deuterium substitution rate". Unless otherwise specified, the "deuterium substitution rate" refers to the ratio of the hydrogen atoms on a single benzene ring connected to the fluorene group or triazine being replaced by deuterium. Since an unsubstituted phenyl group has 5 hydrogen atoms, when the deuterium substitution rate is 20%, 40%, 60%, 80%, or 100%, the corresponding number of deuterium atoms is 1, 2, 3, 4, or 5, respectively.

[0067] In the present application, unless otherwise specified, the term "deuterated phenylene group" refers to a substituted phenylene group formed by replacing at least one hydrogen (H) atom in the phenylene group with a deuterium (D) atom. Without special specification, the number and position of deuterium atoms can be arbitrary. The number of deuterium atoms can be 1, 2, 3, or 4.

[0068] In the present application, unless otherwise specified, the term "phenylene group" refers to a divalent group formed by losing one more hydrogen atom on the basis of the phenyl group, and can also be denoted as "divalent phenyl group". The phenylene group used herein, unless otherwise specified, has two independently single-bond connection sites, and can be represented as -Ph- or The two single-bond connection sites can be ortho-positions (also denoted as 1,2-phenylene, ), para-positions (also denoted as 1,4-phenylene, ), or meta-positions (also denoted as 1,3-phenylene, ).

[0069] Generally, an organic electroluminescent device adopts a sandwich structure, that is, an organic layer is sandwiched between an anode and a cathode on both sides. The organic layer is divided into a hole transport layer, an electron transport layer, a light-emitting layer, a hole blocking layer, an electron blocking layer, etc. according to the different optoelectronic properties of various materials. The electron transport material is a material that transports electrons from the cathode to the light-emitting layer and is an important part of the organic electroluminescent device. Since most organic electroluminescent materials transport holes faster than electrons, the number of electrons and holes in the light-emitting layer is unbalanced, resulting in luminescence quenching and affecting the device performance.

[0070] Some commonly used electron transport materials contain organic compounds such as imidazole groups, thiazole groups, phenanthroline, and thiazole. These compounds generally require good thermal stability and optoelectronic properties. However, it is difficult to obtain a high mobility for organic materials.

[0071] In addition, in traditional technologies, fluorene rings and triazine rings are usually used as the main units in organic electroluminescent materials. Deuterated compounds are usually applied in the host materials and guest materials of light-emitting compounds.

[0072] In the first aspect of the present application, a fluorene-based triazine compound containing a deuterated benzene ring (which can also be denoted as a compound of formula I) is provided, which has the structure shown in formula I:

[0073]

[0074] In formula I, at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1, and Ar2 is a deuterated benzene ring, and L1 is a single bond, a phenylene group, or a deuterated phenylene group.

[0075] In some embodiments, in formula I, R1, R2, R3, R4, R5, R6, and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group, or a deuterated phenyl group.

[0076] In some embodiments, in formula I, R1, R2, R3, R4, R5, R6, and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group, or a deuterated phenyl group; L1 is a single bond, a phenylene group, or a deuterated phenylene group; L2 is a single bond, a phenylene group, or a substituted phenylene group; Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, and a C3-C 30 substituted heteroaryl group; wherein, at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1, and Ar2 is a deuterated benzene ring.

[0077] In some of these embodiments, L2 is a single bond, a phenylene or a substituted phenylene, and in some of these examples, the phenylene in the substituted phenylene may be substituted by 1, 2, 3 or 4 groups selected from the group consisting of a methyl group, a bromine group, a chlorine group and a deuterium atom.

[0078] In some of these embodiments, Ar1 and Ar2 are each independently a C6-C 30 aryl, a C6-C 30 substituted aryl, a C3-C 30 heteroaryl and a C3-C 30 substituted heteroaryl; wherein, the aryl in the C6-C 30 substituted aryl and the heteroaryl in the C3-C 30 substituted heteroaryl are each independently substituted by one or more groups selected from the group consisting of a deuterium atom, a cyano group, a substituted phenyl group and a pyridyl group, and the phenyl in the substituted phenyl group is substituted by one or more cyano groups.

[0079] In some embodiments, in Formula I, R1, R2, R3, R4, R5, R6 and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group or a deuterated phenyl group; L1 is a single bond, a phenylene or a deuterated phenylene;

[0080] L2 is a single bond, a phenylene or a substituted phenylene, wherein the phenylene in the substituted phenylene is substituted by 1, 2, 3 or 4 groups selected from the group consisting of a methyl group, a bromine group, a chlorine group and a deuterium atom;

[0081] Ar1 and Ar2 are each independently a C6-C 30 aryl, a C6-C 30 substituted aryl, a C3-C 30 heteroaryl and a C3-C 30 substituted heteroaryl; wherein, the aryl in the C6-C 30 substituted aryl and the heteroaryl in the C3-C 30 substituted heteroaryl are each independently substituted by one or more groups selected from the group consisting of a deuterium atom, a cyano group, a substituted phenyl group and a pyridyl group, and the phenyl in the substituted phenyl group is substituted by one or more cyano groups;

[0082] Wherein, at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1 and Ar2 is a deuterated benzene ring.

[0083] The present application provides a fluorene-based triazine compound containing a deuterated benzene ring (which can be denoted as the compound of formula I), which contains both a fluorene group and a triazine group in its structure and contains a deuterated benzene ring; the deuterated benzene ring in the compound of formula I may include at least one of a deuterated phenyl group and a deuterated phenylene group. Among them, fluorene has good optoelectronic properties and thermal stability, can effectively enhance the thermal stability of the material, can increase the glass transition temperature of the compound (such as increasing the glass transition temperature to greater than 110 °C), which is beneficial to improving the device life. The triazine group has a strong electronegativity and a high electron mobility, and can effectively improve electron transport and electron injection. By introducing a deuterated benzene ring, the device prepared using this compound can reduce the vibrational energy loss of the compound, improve the exciton-to-photon conversion efficiency, enhance the light-emitting efficiency of the device and extend the life of the device. When the fluorene-based triazine compound containing a deuterated benzene ring is used as an organic electronic material in the organic layer of an organic light-emitting device, based on the synergistic effect of each group in the overall structure of the compound, the light-emitting efficiency of the device can be effectively improved and the service life of the device can be extended.

[0084] In some embodiments, in formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group. At this time, the fluorene-based triazine compound containing a benzene ring can also be denoted as "a compound containing a deuterated phenyl fluorene and a triazine group".

[0085] In some embodiments, in formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group; L1 is a single bond or a phenylene group.

[0086] In some embodiments, in formula I, at least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group; L1 is a single bond or a phenylene group; L2 is a single bond, a phenylene group or a substituted phenylene group; Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group and a C3-C 30 substituted heteroaryl group.

[0087] In formula I, Ar1 and Ar2 may be the same or different.

[0088] The present application also provides a compound containing deuterated phenylfluorene and triazine group, which contains both fluorene group and triazine group in its structure, and a deuterated phenyl group is connected to the fluorene group. Among them, fluorene has a planar biphenyl structure, with strong molecular rigidity, large conjugation degree, high fluorescence quantum efficiency and thermal stability, and is easy to modify, and can be used to improve the electroluminescence performance of OLEDs. The modified materials can be used as hole transport materials and electron transport materials, etc. The introduction of a fluorene group with good optoelectronic properties and thermal stability can effectively enhance the thermal stability of the material, and can increase the glass transition temperature of the compound (such as increasing the glass transition temperature to greater than 110 °C), which is beneficial to improving the device lifetime. The triazine group has a strong electronegativity and high electron mobility, and can effectively improve electron transport and electron injection. By introducing a deuterated phenyl group on the fluorene group, the device prepared from this compound can reduce the vibrational energy loss of the compound, improve the conversion efficiency of excitons to photons, enhance the luminescence efficiency of the device and extend the lifetime of the device. When the compound containing deuterated phenylfluorene and triazine group is used as an organic electronic material in the organic layer of an organic electroluminescent device, based on the synergistic effect of each group in the overall structure of the compound, it can effectively improve the luminescence efficiency of the device and extend the service life of the device.

[0089] Deuterium (D) is an isotope of hydrogen (H). The atomic weight of deuterium is twice that of hydrogen, which results in lower vibrational energy levels of deuterium, making the C-D bond shorter, with a larger bond energy and smaller stretching vibration than the C-H bond. When a hydrogen atom is replaced by a deuterium atom, the chemical properties of the compound can remain almost unchanged; however, due to the atomic weight of deuterium being twice that of hydrogen, the physical properties of the deuterated compound may change. As an example, the vibrational energy levels of the deuterium-substituted compound are reduced. The vibrational energy change based on the deuterium substitution rate of the compound can be obtained through quantum calculation, and the vibrational energy decreases by approximately 2 kilocalories per mole (2 kcal / mol) for each fixed number of deuterium substitutions.

[0090] By carrying out deuteration reaction on the benzene ring (which can be a phenyl group or a phenylene group), the weakening of the intermolecular van der Waals force can be effectively inhibited, or the reduction of the quantum efficiency caused by the collision due to intermolecular vibration can be inhibited. In addition, by replacing the C-H bond with a C-D bond with a larger bond energy, the stability of the compound can also be improved.

[0091] When a fluorene-based triazine compound containing a deuterated benzene ring (which can be, but is not limited to, the compound containing deuterated phenylfluorene and triazine group provided by the present application) is used as at least one of the electron transport material and the hole blocking material of an organic electroluminescent device, it is more beneficial for preparing a device with high efficiency and long lifetime. In addition, it is also beneficial for reducing the driving voltage.

[0092] When a fluorene-based triazine compound containing a deuterated benzene ring (which can be, but is not limited to, the compound containing deuterated phenyl fluorene and a triazine group provided in this application) is used as an electron transport material in an organic electroluminescent device, it is beneficial to the intermolecular stacking during the preparation of the thin film, improves the charge transfer, increases the charge transport ability of the material, and can reduce the operating voltage of the electronic device, and a high-performance device with a low driving voltage, high luminous efficiency, and long device life can be obtained.

[0093] In some embodiments, the fluorene-based triazine compound containing a benzene ring is a compound containing deuterated phenyl fluorene and a triazine group, and it has the structure shown in Formula I;

[0094] In Formula I, at least one of R1, R2, R3, R4, R5, R6, and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, or a tolyl group;

[0095] L1 is a single bond or a phenylene group;

[0096] L2 is a single bond, a phenylene group, or a substituted phenylene group. Optionally, the phenylene group in the substituted phenylene group can be substituted by 1, 2, 3, or 4 groups selected from the following group: a methyl group, a bromo group, a chloro group, and a deuterium atom;

[0097] Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, and any one of a C3-C 30 substituted heteroaryl group; wherein, the aryl group in the C6-C 30 substituted aryl group and the heteroaryl group in the C3-C 30 substituted heteroaryl group are each independently substituted by one or more groups selected from the following group (G1): a deuterium atom, a cyano group, a substituted phenyl group, and a pyridyl group, and the phenyl group in the substituted phenyl group in Group G1 is substituted by one or more groups selected from the following group (G2): a cyano group.

[0098] In some embodiments, L1 is a single bond, a phenylene group, or a deuterated phenylene group.

[0099] In some embodiments, L1 is a single bond or a phenylene group. In some of these embodiments, L1 is a single bond. In some other embodiments, L1 is a phenylene group.

[0100] In some embodiments, L2 is a single bond, a phenylene group, or a substituted phenylene group.

[0101] In some of these embodiments, when L2 is a substituted phenylene group, the phenylene group in the substituted phenylene group can be substituted by 1, 2, 3, or 4 groups selected from the following group: methyl group, bromine group, chlorine group, and deuterium atom; further, the phenylene group in the substituted phenylene group can be substituted by 1, 2, 3, or 4 groups selected from the following group: methyl group, bromine group, and chlorine group.

[0102] In some embodiments, L2 is a single bond or a phenylene group. In some other embodiments, L2 is a substituted phenylene group, and further can be a deuterated phenylene group.

[0103] In some embodiments, L2 is a single bond, or L2 is a phenylene group or a deuterated phenylene group.

[0104] In some embodiments, L2 is a single bond, or L2 is a phenylene group or a deuterated phenylene group; when L2 is a phenylene group or a deuterated phenylene group, the number of deuterium atoms in the deuterated phenylene group is 1, 2, 3, or 4; the two connection sites of L2 are ortho, meta, or para positions.

[0105] In some embodiments, Ar1 and Ar2 are each independently a C6-C 30 aryl group, a C6-C 30 substituted aryl group, a C3-C 30 heteroaryl group, or a C3-C 30 substituted heteroaryl group; wherein, the aryl group in the C6-C 30 substituted aryl group and the heteroaryl group in the C3-C 30 substituted heteroaryl group are each independently substituted by one or more groups selected from the following group (G1): deuterium atom, cyano group, substituted phenyl group, and pyridyl group, and the phenyl group in the substituted phenyl group in group G1 is substituted by 1 or more cyano groups.

[0106] In some embodiments, L2 is a single bond.

[0107] In some embodiments, L1 is a single bond or a phenylene group, and L2 is a single bond or a phenylene group.

[0108] In some embodiments, L1 is a single bond or a phenylene group, and L2 is a single bond.

[0109] In some embodiments, L1 is a single bond or a phenylene group, and L2 is a substituted phenylene group; in some of these embodiments, L2 is a deuterated phenylene group.

[0110] In some embodiments, L2 is a phenylene group or a deuterated phenylene group. In some of these embodiments, the number of deuterium atoms in the deuterated phenylene group can be 1, 2, 3, or 4, and can be respectively referred to as mono-deuterated phenylene group, di-deuterated phenylene group, tri-deuterated phenylene group, or tetra-deuterated phenylene group. The two connection sites of L2 can be ortho, meta, or para positions.

[0111] In some embodiments, each occurrence of "phenylene", unless otherwise specified, the two linking sites can be ortho, meta or para, that is, phenylene can be (1,2-phenylene, ortho form), (1,3-phenylene, meta form) or (1,4-phenylene, para form).

[0112] In some embodiments, L2 is phenylene, optionally 1,4-phenylene (phenylene in para form). In other embodiments, L2 is tetradeuterated phenylene, and further, it can be tetradeuterated phenylene in para form

[0113] In some embodiments, Ar1 and Ar2 are each independently phenyl, deuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, benzonitrile phenyl, pyridyl phenyl, dibenzofuranyl, dibenzothiophenyl, pyridyl or benzonitrile.

[0114] In some embodiments, the aromatic rings in Ar1 and Ar2 are each monocyclic, and the number of monocycles can be one or more. In some of these embodiments, the number of monocycles is more than one, and they are connected to each other by single bonds.

[0115] In the present application, unless otherwise specified, "monocycle" refers to a non-fused ring. As a non-limiting example, biphenyl has two monocycles.

[0116] In some embodiments, Ar1 and Ar2 are each independently phenyl, deuterated phenyl, benzonitrile phenyl, pyridyl phenyl or benzonitrile.

[0117] In the fluorene-based triazine compounds containing deuterated benzene rings provided in the present application, it includes a fluorene group, a triazine group and at least one deuterated benzene ring. The deuterated benzene ring can be located on the fluorene group, or on the triazine group, or also in the linking group between the fluorene group and the triazine group.

[0118] In the compounds containing deuterated phenyl fluorene and triazine group provided in the present application, it includes a fluorene group, a triazine group and at least a deuterated phenyl connected to the fluorene group. The substituents connected to the triazine group may or may not include deuterated phenyl.

[0119] In some embodiments, each occurrence of deuterated phenyl is independently any one group selected from the following group:

[0120]

[0121] In some embodiments, each time a deuterated phenyl group appears, the positions of the deuterium atoms in the deuterated phenyl group can be any part or all of the ortho, para, and meta positions. In some of these embodiments, each time a deuterated phenyl group appears, the positions of the deuterium atoms in the deuterated phenyl group are selected from some or all of the para and meta positions.

[0122] For the deuterated phenyl group linked to the fluorene group, relative to the site in the benzene ring linked to the fluorene ring, the positions of deuterium substitution can be any part or all of the ortho, para, and meta positions of benzene. In some of these preferred examples, the positions of deuterium substitution can be any part or all of the para and meta positions of benzene. It can be understood that the deuterium substitution rate in the deuterated phenyl group is 20% to 100%, and can be 20%, 40%, 60%, 80%, or 100%.

[0123] By selecting different deuterium substitution positions on phenylfluorene (that is, selecting the positions of the deuterium atoms in the deuterated phenyl group linked to the fluorene), the properties of the material can be regulated. Deuterium substitution at the para or meta position of the benzene on the fluorene has a certain impact on the fluorescence efficiency, emission color, and electrical properties of the material, etc. According to the research results, para deuterium substitution can reduce the non-radiative energy loss of the material and improve the fluorescence efficiency; while meta deuterium substitution can change the energy band structure of the material and affect the regulation range of the emission color. For the deuterated phenyl group linked to the fluorene group, as the deuterium substitution rate increases, the fluorescence efficiency of the material may change. Generally speaking, a moderate deuterium substitution rate can improve the stability and lifespan of the material. However, when multiple (two or more) benzene rings are linked to the fluorene ring and the ratio of hydrogen atoms on all benzene rings being deuterated is too high, it may lead to a decrease in the fluorescence efficiency of the material and even affect the luminescence performance of the material. However, when there is only 1 phenyl group in phenylfluorene (that is, when only one benzene ring is linked to the fluorene), the higher the deuterium substitution rate of the phenyl, the better. By selecting an appropriate deuterium substitution rate, better or even optimal material properties can be obtained.

[0124] In some embodiments, the total number of deuterated phenyl groups in R1, R2, R3, R4, R5, R6, and R7 is 1, and the structure of the deuterated phenyl group is (also denoted as pentadeuterated phenyl). In some other embodiments, the total number of deuterated phenyl groups in R1, R2, R3, R4, R5, R6, and R7 is greater than or equal to 2, and the number of deuterium atoms contained in any one deuterated phenyl group is independently 1, 2, 3, or 4.

[0125] In some embodiments, R1 to R7 include at least 3 deuterium atoms, and further, can include at least 5 deuterium atoms. In some of these embodiments, R1 to R7 include 5 to 20 deuterium atoms, and can be optionally 5 to 10 deuterium atoms. For example, it can include 5, 6, 7, 8, 9, or 10 deuterium atoms.

[0126] In this application, unless otherwise specified, "R1 to R7" refers to R1, R2, R3, R4, R5, R6, and R7, and other descriptions such as "R2 to R7" can be understood similarly.

[0127] In some embodiments, R1 is a deuterated phenyl group, R2 is a phenyl group, and R3 to R7 are hydrogen atoms. In some of these embodiments, L1 is a single bond. In some other embodiments, L1 is a phenylene group.

[0128] In some embodiments, R1 and R2 are deuterated phenyl groups, and R3 to R7 are hydrogen atoms. Further, L1 can be a single bond.

[0129] In some embodiments, R6 is a deuterated phenyl group, R1 and R2 are phenyl groups, and R3, R4, R5, and R7 are hydrogen atoms. In some of these embodiments, L1 is a single bond.

[0130] In some embodiments, R7 is a deuterated phenyl group, R1 and R2 are phenyl groups, and R3, R4, R5, and R6 are hydrogen atoms. In some of these embodiments, L1 is a single bond.

[0131] For the deuterated phenyl group connected to the triazine, relative to the site where the benzene ring is connected to the triazine ring, the deuterium substitution position can be selected from any part or all of the ortho, para, and meta positions of the benzene. In some of these embodiments, each time the deuterated phenyl group appears, the position of the deuterium atom in the deuterated phenyl group is selected from part or all of the para and meta positions. It can be understood that the deuterium substitution rate in the deuterated phenyl group is 20% to 100%, and can be 20%, 40%, 60%, 80%, or 100%.

[0132] In the fluorene-based triazine compounds containing deuterated benzene rings provided in this application (which can be, but are not limited to, the compounds containing deuterated phenyl fluorene and triazine groups provided in this application), the triazine ring can play an electron transport role, but is not limited thereto.

[0133] By deuterating the hydrogen atoms on the benzene ring connected to the triazine group, the electronic structure and fluorescence properties of the material can be adjusted. Deuterium substitution at different positions may change the hole transport performance, fluorescence spectrum, charge injection efficiency, etc. of the material. For example, deuterium substitution on the side chain of the triazine group may affect the solubility and film morphology of the material, thereby affecting the processability and performance stability of the device. For the substituents (Ar1 and A) connected to the triazine group r2) The deuterium substitution rate can also affect the properties of the material. Appropriate deuterium substitution can enhance the stability and durability of the material and reduce the degradation and loss of the material. However, when multiple (two or more) benzene rings are connected to the triazine group and the ratio of deuterium substitution of all hydrogen atoms on the benzene rings is too high, it may lead to a decrease in the electron transport performance and luminescence efficiency of the material. On the other hand, increasing the number of deuterations also increases the complexity and cost of the material. By selecting an appropriate number of deuterations, the performance requirements and cost - effectiveness can be balanced.

[0134] In some embodiments, the total number of deuterated phenyl groups in Ar1 and Ar2 is 1, and the structure of the deuterated phenyl group is In other embodiments, the total number of deuterated phenyl groups in Ar1 and Ar2 is greater than or equal to 2, and the number of deuterium atoms contained in any one deuterated phenyl group is independently 1, 2, 3, or 4.

[0135] In some embodiments, Ar1 and Ar2 have 0 to 10 deuterium atoms, which can be 0 deuterium atoms, or 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 deuterium atoms. In some of these embodiments, Ar1 and Ar2 have 5 to 10 deuterium atoms, such as 5, 6, 7, 8, 9, or 10 deuterium atoms.

[0136] In some embodiments, Ar1 and Ar2 each include at least one non - fused benzene ring. The non - fused benzene ring can be a phenyl group or a substituted phenyl group. The substituted phenyl group can be a phenyl group substituted by one or more groups selected from the following group (G1): deuterium atom, cyano group, substituted phenyl group, and pyridyl group. The substituted phenyl group in group G1 can be a phenyl group substituted by one or more cyano groups.

[0137] In some embodiments, Ar1 and Ar2 are each independently a phenyl group, a deuterated phenyl group, a benzyl cyanide phenyl group, a pyridyl phenyl group, or a benzyl cyanide group.

[0138] In the present application, "benzyl cyanide group" can be represented as The substitution position of the cyano group can be at the ortho - position, para - position, or meta - position of the phenyl group. In the present application, "benzyl cyanide phenyl group" can be represented as The substitution position of the benzyl cyanide group can be at the ortho - position, para - position, or meta - position of the phenyl group. Similarly, the pyridyl phenyl group can be represented as The substitution position of the pyridyl group can be at the ortho - position, para - position, or meta - position of the phenyl group.

[0139] In some embodiments, at least one of Ar1 and Ar2 includes a deuterated phenyl group; in some of these embodiments, at least one of Ar1 and Ar2 is a deuterated phenyl group.

[0140] In some embodiments, Ar1 and Ar2 are two phenyl groups. In other embodiments, one of Ar1 and Ar2 is a phenyl group and the other is a deuterated phenyl group (preferably a pentadeuterated phenyl group). In other embodiments, Ar1 and Ar2 are each independently a deuterated phenyl group, and Ar1 and Ar2 may be the same or different; in some of these embodiments, both Ar1 and Ar2 are pentadeuterated phenyl groups, and in some other embodiments, Ar1 and Ar2 are each independently a monodeuterated phenylene group, a dideuterated phenylene group, a trideuterated phenylene group or a tetradeuterated phenylene group. In other embodiments, one of Ar1 and Ar2 is a phenyl group and the other is a benzonitrile phenyl group. In other embodiments, one of Ar1 and Ar2 is a phenyl group and the other is a pyridyl phenyl group.

[0141] In some embodiments, in Formula I, each occurrence of "deuterated phenyl" is any one of R1 to R7, or is Ar1 or Ar2.

[0142] In some embodiments, in Formula I, each occurrence of "deuterated phenyl" may be a low-deuterated phenyl, a medium-deuterated phenyl or a high-deuterated phenyl.

[0143] As used herein, "low-deuterated phenyl" is a deuterated phenyl with a small number of deuterium atoms, generally with a deuterium substitution rate of 20% to 40%, that is, the number of deuterium atoms is 1 to 2, which can be 1 or 2. This substitution form is beneficial to achieving higher luminous efficiency and lower electron transport impedance, with faster electron mobility, and can be used to prepare organic electroluminescent devices with high luminous efficiency and low driving voltage. The deuteration positions in the low-deuterated phenyl can preferably be one or both of the para and meta positions. In some embodiments, the low-deuterated phenyl can be (meta), (para), (meta and para) or (two metas).

[0144] As used herein, "medium-deuterated phenyl" is a deuterated phenyl with a moderate number of deuterium atoms, generally with a deuterium substitution rate of 60% to 80%, that is, the number of deuterium atoms is 3 to 4, which can be 3 or 4. This substitution form is beneficial to achieving better thermal stability and higher photoelectric conversion efficiency, with a higher glass transition temperature of the material and a lower triplet energy level (T1), and can be used to prepare organic electroluminescent devices with high temperature resistance and long luminous lifetime. The deuteration positions in the medium-deuterated phenyl can be one, two or three of the ortho, para and meta positions, and further preferably one or two of the para and meta positions.

[0145] In some embodiments, the medium-deuterated phenyl can be

[0146] As used herein, "highly deuterated phenyl" refers to a phenyl group with a relatively high degree of deuteration, generally having a deuterium substitution rate of 80% to 100%. That is, the number of deuterium atoms is 4 to 5, which can be 4 or 5, and further preferably 5 (corresponding to a deuterium substitution rate of 100%). This substitution form is beneficial for achieving excellent thermal stability, lower charge transport loss, longer lifespan, and a higher glass transition temperature of the material. This is because deuterium substitution can enhance the stability of the bonds within the molecule and reduce the thermal decomposition rate of the molecule, thereby improving the thermal stability of the material. In addition, this substitution form can also make the triplet energy level (T1) lower. This is because the mass of the deuterium atom is heavier. After replacing the hydrogen atom in the phenyl group with a deuterium atom, the vibration frequency of the molecule is reduced, thereby reducing the excited state energy level. The reduced triplet energy level can improve the luminescence efficiency and extend the lifespan. In addition, since deuterium substitution can reduce the vibration and resonance transfer within the molecule, it can reduce the degradation rate of the molecule and extend the lifespan of the material. This substitution form can be used in organic electroluminescent devices with high temperature resistance and long luminescence lifespan. In some embodiments, the highly deuterated phenyl can be

[0147] For the fluorene-based triazine compound containing a deuterated benzene ring provided in the first aspect of the present application (which can be, but is not limited to, the compound containing a deuterated phenyl fluorene and a triazine group provided in the present application), when the ratio of hydrogen atoms replaced by deuterium atoms in its molecule is a low substitution rate (20% to 40%), a medium substitution rate (60% to 80%), and a high substitution rate (such as 100%) respectively, the effects brought about by the increase in the deuterium substitution ratio in the molecule are similar to those brought about by the increase in the deuterium substitution rate in the above-mentioned deuterated phenyl.

[0148] In formula I, when only one deuterated phenyl is connected to the fluorene ring or the triazine ring, the deuterium substitution rate can be preferably 100%, that is When multiple (greater than or equal to 2) deuterated phenyls are connected to the fluorene ring or the triazine ring, the deuterium substitution rate in a single deuterated phenyl can be preferably 20% to 80%. At this time, the number of deuterium atoms in a single deuterated phenyl can be 1, 2, 3, or 4.

[0149] In some embodiments, Ar1 and Ar2 include a cyano-substituted phenyl group (an example of a cyano-substituted phenyl group is a benzonitrile group). The cyano-substituted phenyl group (such as a benzonitrile group) can be directly connected to the triazine ring or indirectly connected to the triazine ring through a linking group (such as a phenylene group, further such as 1,4-phenylene group). For the substituents Ar1 and Ar2 on the triazine group, by introducing a cyano group on the benzene ring, the thermal stability and electron transport properties of the material can be changed, affecting the lifespan of the OLED device. An appropriate amount of cyano substitution can improve the thermal stability and electron transport properties of the material, thereby extending the lifespan of the OLED device. The number of cyano substituents contained in the cyano-substituted phenyl group (such as a benzonitrile group) can be one or more, for example, 1 to 3, further such as 1, 2, or 3, and can preferably be 1. In addition, the cyano substitution position on the benzene ring has a significant impact on the driving voltage. Para substitution is likely to introduce a large electron barrier, resulting in a higher driving voltage; while ortho and meta substitutions introduce smaller electron barriers and lower driving voltages. The substitution position also has an important impact on the conjugation effect and electron transport properties of the material. Para substitution is likely to cause a large conjugation interruption, affecting charge transport and luminescence efficiency; while ortho and meta substitutions can maintain better conjugation, which is beneficial to improving the efficiency of the OLED device. The substitution position also affects the thermal stability and electron transport properties of the material. Para substitution may cause a large torsional strain and change in the energy band structure, thus affecting the thermal stability and lifespan of the material; while ortho and meta substitutions can maintain better molecular structure stability and electron transport properties, which is beneficial to improving the lifespan of the OLED device. In some embodiments, the cyano-substituted phenyl group can be a benzonitrile group, and further can be (ortho), (meta) or (para).

[0150] In some embodiments, Ar1 and Ar2 include pyridyl-substituted phenyl (i.e., pyridylphenyl). The pyridylphenyl can be directly connected to the triazine ring or indirectly connected to the triazine ring through a linking group (such as phenylene, further such as 1,4-phenylene). By introducing pyridyl into the substituents of the triazine group, the electron transport performance of the material can be improved. The substitution position of the pyridyl nitrogen atom has a great influence on the driving voltage of the OLED device. Para-substitution will introduce a large electron barrier, resulting in a higher driving voltage; while ortho- and meta-substitutions introduce smaller electron barriers and lower driving voltages. The substitution position also affects the efficiency of the OLED device. Para-substitution may cause deformation of the molecular structure, leading to changes in the energy band structure and conjugation interruption, thus reducing the charge transport efficiency; while ortho- and meta-substitutions usually can maintain better molecular structure stability and conjugation, which is beneficial to improving the efficiency of the OLED device. The substitution position also has a certain influence on the lifetime of the OLED device. Para-substitution may introduce a large molecular torsional strain, resulting in unstable molecular structure and changes in the energy band structure, thus affecting the thermal stability and lifetime of the material; while ortho- and meta-substitutions usually can maintain better molecular structure stability and electron transport performance, which is beneficial to improving the lifetime of the OLED device. In some embodiments, according to the difference in the pyridyl substitution position, the pyridyl can be (ortho-position), (meta-position) or (para-position).

[0151] In some embodiments, Ar1 and Ar2 are each independently phenyl, deuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, cyano-substituted phenyl-phenyl (such as benzonitrile phenyl), pyridylphenyl, dibenzofuranyl, dibenzothiophenyl, pyridyl or cyano-substituted phenyl (such as benzonitrile).

[0152] In some embodiments, Ar1 and Ar2 are each independently phenyl, deuterated phenyl, cyano-substituted phenyl-phenyl (such as benzonitrile phenyl), pyridylphenyl or cyano-substituted phenyl (such as benzonitrile).

[0153] In some embodiments, Ar1 and Ar2 are each independently phenyl, deuterated phenyl, benzonitrile phenyl, pyridylphenyl or benzonitrile; further, the benzonitrile phenyl can be phenyl substituted by and the pyridylphenyl can be phenyl substituted by ; the benzonitrile can be

[0154] The following is a description of some connection modes between the fluorene ring and the triazine ring.

[0155] In the fluorenyltriazine compounds containing deuterated benzene rings provided in this application (which can be, but are not limited to, the compounds containing deuterated phenylfluorenes and triazine groups provided in this application), the connection position between the fluorene ring and the triazine ring also has a certain influence on the performance of the material. Different connection positions may change the molecular structure, energy band structure, and electron transport properties of the material. By regulating the connection position between fluorene and triazine, spectral regulation, electron energy level adjustment, and charge transport optimization of the material can be achieved.

[0156] In some embodiments, L2 is a single bond. At this time, the fluorene ring and the triazine ring are directly connected. In this connection mode, the fluorene ring and the triazine ring directly connected by a single bond together form a conjugated system. This connection mode can improve the electron transport performance and carrier mobility of the material, thereby improving the efficiency of the OLED device. In addition, the directly connected conjugated system can also improve the fluorescence efficiency and luminescence stability of the material, making it suitable for high-brightness and long-life OLED devices.

[0157] When the fluorene ring and the triazine ring are directly connected (L2 is a single bond), the connection position of the triazine ring on the fluorene ring can be selected at the a-position (1-position), b-position (2-position), or c-position (3-position) on the fluorene ring, respectively, as marked in the following formulas. Different connection positions will have different effects on the performance of the material.

[0158]

[0159] The selection of the direct connection position of the triazine ring on the fluorene ring will affect the performance of the material in aspects such as energy band structure, electron transport performance, fluorescence efficiency, and luminescence color. Factors such as the target performance of the material, synthesis difficulty, and application requirements can be comprehensively considered to select a suitable connection position. When designing and optimizing OLED devices, comparative studies of different position connections can be carried out to obtain the best performance of the electron transport material.

[0160] In some embodiments, L2 is connected to any of the following connection sites:

[0161] (a-position) (b-position) and (c-position).

[0162] Regarding the connection mode at the a-position (1-position): By connecting the triazine ring at the a-position of the fluorene ring, a conjugated system can be formed. This connection mode can improve the electron transport performance and carrier mobility of the material, thereby promoting the effective transport of electrons between the fluorene ring and the triazine ring, which helps to improve the efficiency and performance stability of the OLED device.

[0163] Regarding the b-position (2-position) connection method: By connecting the triazine ring to the b-position of the fluorene ring, a conjugated system can also be formed. Compared with the a-position connection method, the b-position connection method can further adjust the molecular structure and electronic energy level of the material, thereby affecting the photoelectric properties of the material. In more detail, the b-position connection may cause changes in the band structure of the material, thereby affecting the electronic transport performance and fluorescence performance of the material.

[0164] Regarding the c-position (3-position) connection method: By connecting the triazine ring to the c-position of the fluorene ring, a conjugated system can also be formed. Different from the a-position and b-position connection methods, the c-position connection method may change the molecular structure and spatial arrangement of the material, thereby affecting the material's energy band structure and electron transport performance, which may affect the material's fluorescence efficiency and luminescent color.

[0165] In Formula I, L2 may not be a single bond, but may include at least one non-hydrogen atom. In some embodiments, the fluorene ring and the triazine ring may be connected via a benzene ring, and L2 may be a phenylene group or a substituted phenylene group.

[0166] In some embodiments, L2 is a phenylene group, in which case the fluorene ring and the triazine ring are indirectly connected via the phenylene group. By using a phenylene group to connect the fluorene ring and the triazine ring, the distance and relative position between the fluorene ring and the triazine ring can be adjusted, thereby affecting the energy band structure and optoelectronic properties of the material. The phenylene group can be selected in an ortho, meta or para position. Among them, shorter phenylene connections are generally beneficial to improving the electronic transport properties and carrier mobility of the material, but may reduce the fluorescence efficiency of the material. Longer phenylene connections may cause the electronic transport properties of the material to decrease, but help optimize the fluorescence efficiency and luminescent color of the material. In some embodiments, L2 is

[0167] In some embodiments, when the fluorene ring and the triazine ring can be connected through a benzene ring, the hydrogen atoms on the benzene ring can also be replaced by suitable substituents (such as methyl, chloro or bromo). In this case, L2 is a substituted phenylene. Further, the phenylene in the substituted phenylene is substituted by 1 to 4 (such as 1, 2, 3 or 4) groups selected from the following group: methyl, bromo, chloro and deuterium atoms; further, the phenylene in the substituted phenylene is substituted by 1 to 4 (such as 1, 2, 3 or 4) groups selected from the following group: methyl, bromo and chloro. The selection of these substituents will affect the spatial arrangement and relative angle between the fluorene ring and the triazine ring, thereby adjusting the molecular structure and electronic energy level of the material. Different substituent connection methods may lead to differences in the electronic transport properties, fluorescence efficiency and luminescent color of the material.

[0168] In fluorenyltriazine compounds containing deuterated benzene rings (which may be, but are not limited to, the compounds containing deuterated phenylfluorenes and triazine groups provided in this application), the connection position between the fluorene ring and the triazine ring can play an important role in the electron transport materials of organic electroluminescence (OLED). By selecting an appropriate connection position, the energy band structure, electron transport performance, fluorescence efficiency, and emission color of the material can be regulated, thereby optimizing the performance and stability of the OLED device. The connection mode between the fluorene ring and the triazine ring can be reasonably selected and designed according to application requirements and material characteristics.

[0169] In some embodiments, the fluorenyltriazine compound containing a deuterated benzene ring (which may be, but is not limited to, the compound containing deuterated phenylfluorene and triazine group provided in this application) can be any one of the compounds shown in Table 1 below (Compound 1 to Compound 23).

[0170] Table 1. Non-limiting examples of Compounds of Formula I

[0171]

[0172]

[0173]

[0174] Regarding the preparation method of the Compound of Formula I, reference can be made to the respective examples below. Those skilled in the art can prepare the Compound of Formula I according to the structural design of the Compound of Formula I and referring to the preparation methods in the examples below. The synthesized intermediates or products can be separated and purified by column chromatography, and then can be characterized by a nuclear magnetic resonance hydrogen mass spectrometer ( 1 HNMR), a high-resolution mass spectrometer ( 1 HRMS, or denoted as HRMS) and other instruments for molecular structure characterization to identify the molecular structure.

[0175] In the second aspect of this application, an organic electronic material is provided, which contains the fluorenyltriazine compound containing a deuterated benzene ring described in the first aspect of this application (which may be, but is not limited to, the compound containing deuterated phenylfluorene and triazine group provided in this application). This organic electronic material can be used to prepare an organic electroluminescent device and can be introduced into the organic layer of the organic electroluminescent device.

[0176] In the third aspect of this application, an organic electroluminescent device is provided, which includes at least one of the fluorenyltriazine compound containing a deuterated benzene ring described in the first aspect of this application (which may be, but is not limited to, the compound containing deuterated phenylfluorene and triazine group provided in this application) and the organic electronic material described in the second aspect of this application.

[0177] In some embodiments, an organic electroluminescent device is provided, which at least includes an anode, a cathode, and an organic layer; the organic layer includes at least one structural layer among a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer;

[0178] wherein, at least one structural layer in the organic layer contains at least one of the fluorene-based triazine compounds containing a deuterated benzene ring described in the first aspect of the present application (which may be, but is not limited to, the compounds provided in the present application containing deuterated phenylfluorene and triazine groups) and at least one of the organic electronic materials described in the second aspect of the present application.

[0179] In some embodiments, the total thickness of the organic layer is 1 nm to 1000 nm; further optionally, the total thickness of the organic layer is 50 nm to 500 nm.

[0180] In some embodiments, a substrate is provided on the side of the anode away from the organic layer, which may be a glass substrate, and further may be a glass substrate.

[0181] In some embodiments, the organic electroluminescent device (for reference, see Figure 1 ) includes a glass substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, an electron blocking layer 150, a light-emitting layer 160, a hole blocking layer 170, an electron transport layer 180, an electron injection layer 190, and a cathode 200, which are sequentially stacked.

[0182] In some embodiments, the organic layer includes at least one structural layer among a hole blocking layer and an electron transport layer; wherein, at least one structural layer among the hole blocking layer and the electron transport layer contains the aforementioned fluorene-based triazine compounds containing a deuterated benzene ring (which may be, but is not limited to, the compounds provided in the present application containing deuterated phenylfluorene and triazine groups) and at least one of the organic electronic materials.

[0183] In some embodiments, the organic electroluminescent device is a single electron device, and the organic layer includes at least one structural layer among a hole injection layer, an electron transport layer, and an electron injection layer.

[0184] In some embodiments, the organic electroluminescent device is a single electron device (for reference, see Figure 2 ), and includes an anode 120, a hole injection layer 130, an electron transport layer 180, an electron injection layer 190, and a cathode 200, which are sequentially stacked.

[0185] In some embodiments, the organic electroluminescent device includes an electron transport layer, and the electron transport layer contains at least one of the aforementioned fluorene-based triazine compounds containing a deuterated benzene ring (which may be, but is not limited to, the compounds provided in the present application containing deuterated phenylfluorene and triazine groups) and at least one of the organic electronic materials.

[0186] In the fourth aspect of the present application, there is provided the use of the fluorene-based triazine compound containing a deuterated benzene ring described in the first aspect of the present application (which may be, but is not limited to, the compound containing a deuterated phenyl fluorene and a triazine group provided by the present application) or the organic electronic material described in the second aspect of the present application, including at least the use in the preparation of an organic electroluminescent device.

[0187] In some embodiments, the organic electronic material containing the compound of Formula I is used as an electron transport material in an organic electroluminescent device. In some of these embodiments, the organic electronic material or the electron transport layer may be doped with an organometallic complex. Non-limiting examples of the organometallic complex include lithium 8-hydroxyquinolate (denoted as Liq or LiQ). Regarding the doping amount of the organometallic complex, the mass content of the organometallic complex in the organic electronic material or the electron transport layer may be 20 wt% to 70 wt%, and may also be any one of the following percentages, or a range selected from any two of the following percentages: 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc. In some embodiments, non-limitingly, the organic electronic material or the electron transport layer includes lithium 8-hydroxyquinolate. Further, the mass content of lithium 8-hydroxyquinolate in the organic electronic material or the electron transport layer may be 20 wt% to 70 wt%, and may also be any one of the following percentages, or a range selected from any two of the following percentages: 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc.

[0188] In some embodiments, the organic electroluminescent device includes a hole blocking material. Non-limitingly, the hole blocking material may include one or more compounds among the compounds (HB-1 to HB-14) in Table 2 below. By introducing the compounds in Table 2 into the hole blocking layer, it is more beneficial to reduce the driving voltage, improve the current efficiency, and extend the device life.

[0189] In some embodiments, the hole blocking layer contains one or more compounds among the compounds (HB-1 to HB-14) in Table 2 below. In some of these examples, the hole blocking layer includes a hole blocking material, and the hole blocking material is one or more of the compounds (HB-1 to HB-14) in Table 2.

[0190] Table 2.

[0191]

[0192]

[0193]

[0194] In the organic electroluminescent device provided by the present application, the light-emitting layer can provide good light-emitting characteristics by adjusting the range of visible light as needed. The light-emitting layer may contain one or more of the following compounds: including but not limited to naphthalene compounds, pyrene compounds, fluorene compounds, phenanthrene compounds, chrysene compounds, fluoranthene compounds, anthracene compounds, pentacene compounds, perylene compounds, diarylethene compounds, triphenylamine-ethylene compounds, amine compounds, carbazole compounds, benzimidazole compounds, furan compounds, metal-organic fluorescent complexes, metal-organic phosphorescent complexes (such as organophosphorescent complexes of metal elements such as iridium (Ir), platinum (Pt), osmium (Os), copper (Cu), gold (Au), etc.), boron-nitrogen compounds, polyvinylcarbazole, polyorganosilicon compounds, polythiophene and other organic polymer light-emitting materials. These light-emitting materials can be used alone or in combination of multiple mixtures.

[0195] In the organic electroluminescent device provided by the present application, each layer of the organic layer can be prepared by vacuum evaporation, molecular beam evaporation, dip coating method dissolved in a solvent, spin coating method, bar coating method or inkjet printing method. For metal electrodes, evaporation method or sputtering method can be used for preparation.

[0196] The compound of formula I provided by the present application and the organic electronic material containing the compound of formula I can also be applied to at least one of organic solar cells, organic thin film transistors, organic photodetectors, organic field effect transistors, organic integrated circuits and organic photoreceptors.

[0197] The embodiments of the present application will be described in detail below in conjunction with some examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. For the experimental methods without specified conditions in the following examples, the guidance given in the present application is preferably referred to, and it can also be carried out according to the experimental manuals or conventional conditions in the art, or according to the conditions recommended by the manufacturer, or referring to the experimental methods known in the art.

[0198] The following examples provide a preparation method of the compound of formula I (a fluorene-based triazine compound containing a deuterated benzene ring, which can be but not limited to the compound containing a deuterated phenylfluorene and a triazine group provided by the present application), including the synthesis methods of some intermediates and / or compounds. The synthesized intermediates or products are separated by column chromatography, and then the molecular structures are characterized by nuclear magnetic resonance hydrogen mass spectrometry ( 1 HNMR) and high-resolution mass spectrometry (HRMS).

[0199] In the following examples, "room temperature" means 23°C to 27°C. eq represents molar equivalent. "The synthesis method is the same as that of compound C" means that the synthesis is carried out using the same mechanism and basically the same synthesis route as that of compound C, except that the corresponding raw materials are selected according to the different target compounds.

[0200] CDCl3 represents deuterated chloroform.

[0201] I. Preparation of a fluorene-based triazine compound containing a deuterated benzene ring (Compound of Formula I), which may be, but is not limited to, a compound containing a deuterated phenylfluorene and a triazine group.

[0202] Preparation Example 1. Preparation of Compound 1

[0203]

[0204] 1.1. Synthesis of Intermediate 1-1

[0205] Add 2-bromobenzofluorone (20.0 g, 77.19 mmol, denoted as 1 eq) and tetrahydrofuran (100 mL) to a three-necked flask, stir at room temperature, and dropwise add a phenylmagnesium bromide solution (1.6 M, 120 mL, approximately 2.5 eq) under nitrogen protection. After stirring and reacting for 3 h, the reaction is complete. Dropwise add a dilute hydrochloric acid solution until the pH of the aqueous phase is weakly acidic (pH 4 - 6), separate the layers, concentrate the organic phase, and separate the crude product by column chromatography to obtain 21.5 g of a colorless oily liquid with a yield of 82%. HRMS (ESI, m / z): [M - H] + : C 19 H 12 BrO, the theoretical value (calcd) is 335.0077, and the measured value (found) is 335.0072.

[0206] 1.2. Synthesis of Intermediate 1-2

[0207] Place perdeuterated benzene (10.5 g, 124.78 mmol) and dichloromethane (200 mL) in a three-necked flask, add anhydrous aluminum trichloride (16.2 g, 121.50 mmol) under nitrogen protection, and then dropwise add a dichloromethane (60 mL) solution of Intermediate 1-1 (21.0 g, 62.27 mmol). Stir and react at room temperature for 5 h, quench the reaction by dropwise adding a dilute hydrochloric acid aqueous solution, separate the layers, and concentrate the organic phase to dryness. The crude product is passed through a column with 100 mL of petroleum ether to obtain 13.6 g of a white solid with a yield of 54%. HRMS (ESI, m / z): [M] + calcd for: C 25 H 12 D5Br, 401.0827, found, 401.0833.

[0208] 1.3. Synthesis of Intermediate 1-3

[0209] Intermediate 1-2 (13 g, 32.31 mmol), bis(pinacolato)diboron (9.8 g, 38.59 mmol), potassium acetate (9.5 g, 96.80 mmol) and anhydrous toluene (130 mL) were placed in a three-necked flask. Under nitrogen protection, dichlorobis(triphenylphosphine)palladium(II) (Pd(PPh3)2Cl2, 0.26 g, 0.37 mmol) was added. The mixture was refluxed for 5 h, filtered, concentrated to dryness, and separated by column chromatography to obtain 12.5 g of a white solid with a yield of 86%. HRMS (ESI, m / z): [M+H] + calcd for: C 31 H 25 D5BO2, 450.2647, found, 450.2653。

[0210] 1.4. Synthesis of Compound 1

[0211] 2-Chloro-4,6-diphenyl-1,3,5-triazine (1 g, 3.74 mmol), Intermediate 1-3 (1.76 g, 3.92 mmol) and potassium carbonate (1.0 g, 7.24 mmol) were added to a three-necked flask. Then, toluene (10 mL), tetrahydrofuran (5 mL) and deionized water (5 mL) were added. Under nitrogen protection, dichlorobis(triphenylphosphine)palladium(II) (0.01 g, 0.014 mmol) was added. After refluxing for 10 h, a solid precipitated. The solid was filtered, washed with ethanol, and the crude product was separated by column chromatography. Elution with PE / DCM = 1 / 2, concentrated to dryness, and dried to obtain 1.56 g of a white solid with a yield of 75%. 1 H NMR (400 MHz, CDCl3) δ: 8.20 - 8.24 (m, 4H), 7.99 - 8.02 (m, 1H), 7.77 - 7.85 (m, 3H), 7.34 - 7.45 (m, 8H), 7.25 - 7.32 (m, 4H), 7.11 - 7.15 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 40 H 23 D5N3, 555.2592, found, 555.2598. Anal.: calcd: C, 86.45; H, 5.98; N, 7.56; found: C, 86.56; H, 5.84; N, 7.61。

[0212] Preparation Example 2. Preparation of Compound 2

[0213]

[0214] 2.1. Synthesis of Intermediate 2-1

[0215] The synthesis method is the same as that of intermediate 1-1, with a yield of 80%. HRMS(ESI, m / z): [M-H] + calcd for: C 19 H7D5BrO, 340.0391, found, 340.0388。

[0216] 2.2. Synthesis of intermediate 2-2

[0217] The synthesis method is the same as that of intermediate 1-2, with a yield of 61%. HRMS(ESI, m / z): [M] + calcd for: C 25 H7D 10 Br, 406.1141, found, 406.1135。

[0218] 2.3. Synthesis of intermediate 2-3

[0219] The synthesis method is the same as that of intermediate 1-3, with a yield of 89%. HRMS(ESI, m / z): [M+H] + calcd for: C 31 H 20 D 10 BO2, 455.2961, found, 455.2967。

[0220] 2.4. Synthesis of compound 2

[0221] The synthesis method is the same as that of compound 1, with a yield of 72%. 1 H NMR(400MHz, CDCl3) δ: 8.20 - 8.24(m, 4H), 8.00 - 8.03(m, 1H), 7.79 - 7.85(m, 3H), 7.35 - 7.45(m, 8H), 7.28 - 7.32(m, 1H). HRMS(ESI, m / z): [M+H] + calcd for: C 40 H 18 D 10 N3, 560.2905, found, 560.2902. Anal.: calcd: C, 85.83; H, 6.66; N, 7.51; found: C, 85.74; H, 6.70; N, 7.58。

[0222] Preparation Example 3. Preparation of compound 3

[0223] 3.1. Synthesis of intermediate 3-1

[0224] 2-Bromo-4'-chloro-1,1'-biphenyl (5.0 g, 18.69 mmol), magnesium turnings (2.0 g, 82.27 mmol) and tetrahydrofuran (10 mL) were added to a three-necked flask, and then 2 iodine grains were added. Under nitrogen protection, the reaction was initiated by heating with a hair dryer until the color of iodine faded. Under reflux, a solution of 2-bromo-4'-chloro-1,1'-biphenyl (15.0 g, 56.06 mmol) in tetrahydrofuran (50 mL) was added dropwise. After stirring the reaction for 3 h, the magnesium turnings were almost completely reacted. The Grignard solution was poured into a dropping funnel and added dropwise to a solution of tribromobenzophenone (10 g, 38.30 mmol) in tetrahydrofuran (THF, 40 mL) under reflux. After refluxing for 3 h, the reaction was complete. It was cooled, and dilute hydrochloric acid aqueous solution was added dropwise until the pH of the aqueous phase was weakly acidic (pH 4 - 6). After liquid separation, the organic phase was concentrated to dryness, and the crude product was separated by column chromatography to obtain 12.5 g of a colorless oily liquid with a yield of 72%. HRMS (ESI, m / z): [M-H] + calcd for: C 25 H 17 BrClO, 447.0157, found, 447.0158。

[0225]

[0226] 3.2. Synthesis of Intermediate 3-2

[0227] Intermediate 3-1 (12.0 g, 26.68 mmol), glacial acetic acid (60 mL) and concentrated hydrochloric acid (5 mL) were placed in a single-necked flask, and the reaction was stirred under reflux for 5 h. After the reaction was complete, the solvent was concentrated to dryness. The crude product was separated by column chromatography to obtain 10.5 g of a white solid with a yield of 91%. HRMS (ESI, m / z): [M] + calcd for: C 25 H 16 BrCl, 430.0124, found, 430.0126。

[0228] 3.3. Synthesis of Intermediate 3-3

[0229] Intermediate 3-2 (10.0 g, 23.16 mmol), phenylboronic acid-d5 (3.2 g, 25.20 mmol) and potassium carbonate (4.8 g, 34.73 mmol) were placed in a three-necked flask, and then toluene (60 mL), ethanol (30 mL) and deionized water (30 mL) were added. Under nitrogen protection, Pd(PPh3)2Cl2 (0.2 g, 0.28 mmol) was added, and the reaction was stirred under reflux for 5 h. After the reaction was complete, it was cooled, and liquid separation was carried out. The organic phase was concentrated to dryness. The crude product was separated by column chromatography to obtain 8.7 g of a white solid with a yield of 86%. HRMS (ESI, m / z): [M]+ Calculated for: C 31 H 16 D5Cl, 433.1646, found, 433.1653。

[0230] 3.4. Synthesis of Intermediate 3-4

[0231] Intermediate 3-3 (8.0 g, 18.43 mmol), bis(pinacolato)diboron (5.6 g, 22.05 mmol), potassium acetate (5.4 g, 55.02 mmol) and anhydrous toluene (80 mL) were placed in a three-necked flask. Under nitrogen protection, Pd2(dba)3 (0.12 g, 0.13 mmol) was added, and the mixture was refluxed for 5 h, filtered, concentrated to dryness, and separated by column chromatography to obtain 8.3 g of a white solid with a yield of 85%. HRMS (ESI, m / z): [M+H] + Calculated for: C 37 H 29 D5BO2, 526.2960, found, 526.2968。

[0232] 3.5. Synthesis of Compound 3

[0233] The synthesis method was the same as that of Compound 1, with a yield of 81%. 1 1H NMR (400 MHz, CDCl3) δ: 8.16 - 8.20 (m, 4H), 7.98 - 8.01 (m, 1H), 7.82 - 7.91 (m, 3H), 7.34 - 7.47 (m, 11H), 7.22 - 7.32 (m, 4H), 7.17 - 7.21 (m, 2H), 7.07 - 7.10 (m, 1H). HRMS (ESI, m / z): [M+H] + Calculated for: C 46 H 27 D5N3, 631.2905, found, 631.2898. Anal.: calculated: C, 87.59; H, 5.75; N, 6.66; found: C, 87.65; H, 5.62; N, 6.69。

[0234] Preparation Example 4. Synthesis of Compound 4

[0235]

[0236] The synthesis method was similar to that of Compound 3, with a yield of 83%. 11H NMR (400 MHz, CDCl3) δ: 8.14 - 8.21 (m, 4H), 7.95 - 8.07 (m, 1H), 7.87 - 7.96 (m, 3H), 7.31 - 7.48 (m, 11H), 7.12 - 7.35 (m, 4H), 7.14 - 7.21 (m, 2H), 7.07 - 7.14 (m, 1H). HRMS (ESI, m / z): [M + H] + calcd for: C 46 H 27 D5N3, 632.2905, found, 631.2854. Anal.: calcd: C, 87.59; H, 5.75; N, 6.60; found: C, 87.63; H, 5.65; N, 6.64。

[0237] Preparation Example 5. Preparation of Compound 5

[0238]

[0239] 5.1. Synthesis of Intermediate 5-1

[0240] The synthesis method is the same as that of Intermediate 1-1, with a yield of 77%. HRMS (ESI, m / z): [M - H] + calcd for: C 19 H 11 BrClO, 368.9687, found, 368.9689。

[0241] 5.2. Synthesis of Intermediate 5-2

[0242] The synthesis method is the same as that of Intermediate 1-2, with a yield of 55%. HRMS (ESI, m / z): [M] + calcd for: C 25 H 16 BrCl, 430.0124, found, 430.0128。

[0243] 5.3. Synthesis of Intermediate 5-3

[0244] The synthesis method is the same as that of Intermediate 3-3, with a yield of 90%. HRMS (ESI, m / z): [M] + calcd for: C 31 H 16 D5Cl, 433.1646, found, 433.1641。

[0245] 5.4. Synthesis of Intermediate 5-4

[0246] The synthesis method is the same as that of intermediate 3-4, with a yield of 85%. HRMS (ESI, m / z): [M+H] + calcd for: C 37 H 29 D5BO2, 526.2960, found, 526.2957

[0247] 5.5. Synthesis of Compound 5

[0248] The synthesis method is the same as that of Compound 1, with a yield of 68%. 1 H NMR (400 MHz, CDCl3) δ: 8.17 - 8.20 (m, 4H), 8.02 - 8.05 (m, 1H), 7.78 - 7.82 (m, 2H), 7.36 - 7.45 (m, 7H), 7.22 - 7.32 (m, 7H), 7.17 - 7.21 (m, 4H), 6.86 - 6.88 (m, 1H). HRMS (ESI, m / z): [M+H] + calcd for: C 46 H 27 D5N3, 631.2905, found, 631.2907. Anal.: calcd: C, 87.59; H, 5.75; N, 6.66; found: C, 87.46; H, 5.84; N, 6.71

[0249] Preparation Example 6. Synthesis of Compound 7

[0250]

[0251] The synthesis method is the same as that of Compound 1, with a yield of 63%. 1 H NMR (400 MHz, CDCl3) δ: 8.19 - 8.22 (m, 2H), 8.01 - 8.03 (m, 1H), 7.76 - 7.85 (m, 3H), 7.35 - 7.45 (m, 5H), 7.25 - 7.29 (m, 4H), 7.11 - 7.14 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 40 H 18 D 10 N3, 560.2905, found, 560.2901. Anal.: calcd: C, 85.83; H, 6.66; N, 7.51; found: C, 85.72; H, 6.79; N, 7.45

[0252] Preparation Example 7. Synthesis of Compound 8

[0253]

[0254] The synthesis method is the same as that of Compound 1, and the yield is 60%. 1 H NMR(400MHz,CDCl3)δ:8.01 - 8.03(m,1H),7.76 - 7.85(m,3H),7.35 - 7.39(m,2H),7.25 - 7.31(m,4H),7.11 - 7.15(m,2H).HRMS(ESI,m / z):[M+H] + calcd for:C 40 H 13 D 15 N3,565.3219,found,565.3222.Anal.:calcd:C,85.07;H,7.49;N,7.44;found:C,84.98;H,7.55;N,7.42。

[0255] Preparation Example 8. Synthesis of Compound 9

[0256]

[0257] The synthesis method is the same as that of Compound 1, and the yield is 72%. 1 H NMR(400MHz,CDCl3)δ:8.17 - 8.24(m,4H),7.99 - 8.02(m,1H),7.77 - 7.85(m,3H),7.66 - 7.76(m,5H),7.50 - 7.53(m,1H),7.33 - 7.44(m,5H),7.25 - 7.31(m,4H),7.08 - 7.12(m,2H).HRMS(ESI,m / z):[M+H] + calcd for:C 47 H 26 D5N4,656.2857,found,656.2859.Anal.:calcd:C,86.08;H,5.38;N,8.54;found:C,86.01;H,5.45;N,8.60。

[0258] Preparation Example 9. Synthesis of Compound 10

[0259] Compound 10 was synthesized by a method substantially the same as that for synthesizing Compound 1, and the yield was 62%. 11H NMR (400 MHz, CDCl3) δ: 8.74 - 8.79 (m, 2H), 8.22 - 8.27 (m, 4H), 7.70 - 7.85 (m, 2H), 7.45 - 7.76 (m, 5H), 7.53 - 7.58 (m, 1H), 7.43 - 7.68 (m, 5H), 7.23 - 7.38 (m, 4H), 7.21 - 7.27 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 47 H 25 D5N4, 645.2050, found, 632.4854. Anal.: calcd: C, 85.51; H, 5.52; N, 8.81; found: C, 85.87; H, 5.64; N, 8.98。

[0260]

[0261] Preparation Example 10. Synthesis of Compound 11

[0262]

[0263] Compound 11 was synthesized by a method substantially the same as that for synthesizing Compound 1, with a yield of 64%. 1 1H NMR (400 MHz, CDCl3) δ: 8.73 - 8.79 (m, 2H), 8.22 - 8.26 (m, 4H), 7.70 - 7.85 (m, 2H), 7.45 - 7.76 (m, 5H), 7.53 - 7.58 (m, 1H), 7.43 - 7.68 (m, 5H), 7.23 - 7.38 (m, 4H), 7.21 - 7.27 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 47 H 25 D5N4, 645.2073, found, 635.3642. Anal.: calcd: C, 85.53; H, 5.51; N, 8.81; found: C, 85.86; H, 5.68; N, 8.97。

[0264] Preparation Example 11. Synthesis of Compound 12

[0265]

[0266] The synthesis method was the same as that for Compound 1, with a yield of 68%. 11H NMR (400 MHz, CDCl3) δ: 8.78 - 8.80 (m, 2H), 8.17 - 8.23 (m, 4H), 7.99 - 8.02 (m, 1H), 7.70 - 7.85 (m, 6H), 7.55 - 7.58 (m, 1H), 7.33 - 7.45 (m, 5H), 7.23 - 7.31 (m, 4H), 7.09 - 7.12 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 45 H 26 D5N4, 632.2857, found, 632.2854. Anal.: calcd: C, 85.55; H, 5.58; N, 8.87; found: C, 85.44; H, 5.62; N, 8.93。

[0267] Preparation Example 12. Synthesis of Compound 14

[0268]

[0269] Compound 14 was synthesized by a method substantially the same as that for synthesizing Compound 2, with a yield of 72%. 1 1H NMR (400 MHz, CDCl3) δ: 8.73 - 8.79 (m, 2H), 8.22 - 8.26 (m, 4H), 7.70 - 7.85 (m, 2H), 7.45 - 7.76 (m, 5H), 7.53 - 7.58 (m, 1H), 7.43 - 7.68 (m, 5H), 7.23 - 7.38 (m, 4H), 7.21 - 7.27 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 40 H 21 D6N3, 543.1773, found, 530.3645. Anal.: calcd: C, 80.14; H, 5.21; N, 7.81; found: C, 78.86; H, 4.88; N, 7.47。

[0270] Preparation Example 13. Synthesis of Compound 19

[0271]

[0272] The synthesis method was the same as that for Compound 1, with a yield of 65%. 11H NMR (400 MHz, CDCl3) δ: 8.98 - 8.99 (m, 1H), 8.62 - 8.65 (m, 1H), 8.16 - 8.28 (m, 4H), 7.99 - 8.02 (m, 2H), 7.77 - 7.85 (m, 3H), 7.67 - 7.71 (m, 1H), 7.47 - 7.50 (m, 1H), 7.33 - 7.45 (m, 6H), 7.23 - 7.31 (m, 4H), 7.09 - 7.12 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 45 H 26 D5N4, 632.2857, found, 632.2852. Anal.: calcd: C, 85.55; H, 5.58; N, 8.87; found: C, 85.59; H, 5.53; N, 8.85。

[0273] Preparation Example 14. Synthesis of Compound 21

[0274]

[0275] Compound 21 was synthesized by a method substantially the same as that for synthesizing Compound 1, with a yield of 65%. 1 1H NMR (400 MHz, CDCl3) δ: 8.74 - 8.79 (m, 2H), 8.22 - 8.27 (m, 4H), 7.70 - 7.85 (m, 2H), 7.45 - 7.76 (m, 5H), 7.53 - 7.58 (m, 1H), 7.43 - 7.68 (m, 5H), 7.23 - 7.38 (m, 4H), 7.21 - 7.27 (m, 2H). HRMS (ESI, m / z): [M+H] + calcd for: C 51 H 29 D4N4, 697.2390, found, 630.4783. Anal.: calcd: C, 87.91; H, 6.02; N, 8.91; found: C, 85.82; H, 5.84; N, 8.65。

[0276] Preparation Example 15. Synthesis of Compound 22

[0277]

[0278] Compound 22 was synthesized by a method substantially the same as that for synthesizing Compound 21, with a yield of 68%. 11H NMR (400 MHz, CDCl3) δ: 8.74 - 8.79 (m, 2H), 8.22 - 8.27 (m, 4H), 7.70 - 7.85 (m, 2H), 7.45 - 7.76 (m, 5H), 7.53 - 7.58 (m, 1H), 7.43 - 7.68 (m, 5H), 7.23 - 7.38 (m, 4H), 7.21 - 7.27 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 51 H 29 D4N4, 697.2390, found, 630.7856. Anal.: calcd: C, 87.97; H, 6.12; N, 8.89; found: C, 85.87; H, 5.81; N, 8.63。

[0279] Preparation Example 16. Synthesis of Compound 23

[0280]

[0281] Compound 23 was synthesized by a method substantially the same as that for synthesizing Compound 1, with a yield of 66%. 1 1H NMR (400 MHz, CDCl3) δ: 8.72 - 8.78 (m, 2H), 8.21 - 8.25 (m, 4H), 7.69 - 7.87 (m, 2H), 7.45 - 7.75 (m, 5H), 7.52 - 7.55 (m, 1H), 7.43 - 7.65 (m, 5H), 7.21 - 7.36 (m, 4H), 7.19 - 7.22 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 46 H 26 D5N3, 632.2850, found, 632.2852. Anal.: calcd: C, 85.51; H, 5.52; N, 8.81; found: C, 85.47; H, 5.66; N, 8.90。

[0282] Preparation Example 17. Synthesis of Compound 24

[0283]

[0284] 17.1. Synthesis of Intermediate 6 - 1

[0285] Benzene (10.5 g, 124.78 mmol) and dichloromethane (200 mL) were placed in a three-necked flask. Anhydrous aluminum trichloride (16.2 g, 121.50 mmol) was added under nitrogen protection, and then a dichloromethane (60 mL) solution of intermediate 1-1 (21.0 g, 62.27 mmol) was added dropwise. The reaction was stirred at room temperature for 5 h, quenched by adding dilute hydrochloric acid aqueous solution, separated by liquid-liquid extraction, and the organic phase was concentrated to dryness. The crude product was purified by column chromatography with 100 mL of petroleum ether to obtain 12.8 g of a white solid with a yield of 51%. HRMS (ESI, m / z): [M] + calcd for: C 25 H 17 Br, 390.0157, found, 389.0743。

[0286] 17.2. Synthesis of intermediate 6-2

[0287] Intermediate 6-1 (13 g, 32.31 mmol), bis(pinacolato)diboron (9.8 g, 38.59 mmol), potassium acetate (9.5 g, 96.80 mmol) and anhydrous toluene (130 mL) were placed in a three-necked flask. Dichlorobis(triphenylphosphine)palladium(II) (Pd(PPh3)2Cl2, 0.26 g, 0.37 mmol) was added under nitrogen protection, and the mixture was refluxed for 5 h, filtered, concentrated to dryness, and separated by column chromatography to obtain 12.1 g of a white solid with a yield of 82%. HRMS (ESI, m / z): [M + H] + calcd for: C 31 H 30 BO2, 451.2721, found, 447.2253。

[0288] 17.3. Synthesis of compound 24

[0289] 2-Chloro-4-phenyl-6-deuterophenyl-1,3,5-triazine (1.2 g, 3.74 mmol), intermediate 6-2 (1.67 g, 3.90 mmol) and potassium carbonate (1.0 g, 7.24 mmol) were added to a three-necked flask, followed by toluene (10 mL), tetrahydrofuran (5 mL) and deionized water (5 mL). Dichlorobis(triphenylphosphine)palladium(II) (0.01 g, 0.014 mmol) was added under nitrogen protection, and the mixture was refluxed for 10 h. A solid precipitated, was filtered, washed with ethanol, and the crude product was separated by column chromatography, eluted with PE / DCM = 1 / 2, concentrated to dryness, and dried to obtain 1.56 g of a white solid with a yield of 75%. 11H NMR (400 MHz, CDCl3) δ: 8.20 - 8.24 (m, 4H), 7.99 - 8.02 (m, 1H), 7.77 - 7.85 (m, 3H), 7.34 - 7.45 (m, 8H), 7.25 - 7.32 (m, 4H), 7.11 - 7.15 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 40 H 23 D5N3, 555.2592, found, 555.2598. Anal.: calcd: C, 86.45; H, 5.98; N, 7.56; found: C, 86.56; H, 5.84; N, 7.61.

[0290] Preparation Example 18. Synthesis of Compound 25

[0291]

[0292] 2 - (3 - Chlorodeuterophenyl) - 4,6 - diphenyl - 1,3,5 - triazine (1.2 g, 3.74 mmol), Intermediate 6 - 2 (1.67 g, 3.90 mmol) and potassium carbonate (1.0 g, 7.24 mmol) were added to a three - necked flask, followed by the addition of toluene (10 mL), tetrahydrofuran (5 mL) and deionized water (5 mL). Under nitrogen protection, bis(triphenylphosphine)palladium(II) chloride (0.01 g, 0.014 mmol) was added. After refluxing for 10 h, a solid precipitated. The solid was filtered, washed with ethanol, and the crude product was separated by column chromatography, eluting with PE / DCM = 1 / 2. After concentration to dryness and drying, 1.56 g of a white solid was obtained with a yield of 75%. 1 1H NMR (400 MHz, CDCl3) δ: 8.20 - 8.24 (m, 4H), 7.99 - 8.02 (m, 1H), 7.77 - 7.85 (m, 3H), 7.34 - 7.45 (m, 8H), 7.25 - 7.32 (m, 4H), 7.11 - 7.15 (m, 2H). HRMS (ESI, m / z): [M + H] + calcd for: C 46 H 28 D5N3, 564.7172, found, 564.2495. Anal.: calcd: C, 92.45; H, 5.98; N, 7.56; found: C, 92.46; H, 5.81; N, 7.64.

[0293] Preparation Example 19. Preparation of Compound 26

[0294]

[0295] 19.1. Synthesis of Intermediate 7-1

[0296] The synthesis method is the same as that of Intermediate 1-1, with a yield of 75%. HRMS (ESI, m / z): [M-H] + calcd for: C25H8OBr, 402.9823, found, 345.0388。

[0297] 19.2. Synthesis of Intermediate 7-2

[0298] The synthesis method is the same as that of Intermediate 6-1, with a yield of 65%. HRMS (ESI, m / z): [M] + calcd for: C31H12Br, 463.0145, found, 416.1235。

[0299] 19.3. Synthesis of Intermediate 7-3

[0300] The synthesis method is the same as that of Intermediate 6-2, with a yield of 82%. HRMS (ESI, m / z): [M+H] + calcd for: C37H24O2B, 511.1869, found, 457.2967。

[0301] 19.4. Synthesis of Compound 26

[0302] The synthesis method is the same as that of Compound 6, with a yield of 70%. 1 H NMR (400 MHz, CDCl3) δ: 8.20 - 8.24 (m, 4H), 8.00 - 8.03 (m, 1H), 7.79 - 7.85 (m, 3H), 7.35 - 7.45 (m, 8H), 7.28 - 7.32 (m, 1H). HRMS (ESI, m / z): [M+H] + calcd for: C46H22N3, 616.1814, found, 57660.2902. Anal.: calcd: C, 85.83; H, 6.66; N, 7.51; found: C, 85.74; H, 6.70; N, 7.58。

[0303] II. Preparation of Organic Electroluminescent Devices

[0304] The structures and properties of the organic electroluminescent devices prepared using the Compound of Formula I of the present application are further described in detail below through Examples 1 to 18. The corresponding preparation methods can also be used to prepare the samples required for some subsequent test examples. Except for the Compound of Formula I, the organic materials used can be obtained commercially or prepared and their structures identified by referring to the method for synthesizing the Compound of Formula I.

[0305] Examples 1 to 18 used a fluorene-based triazine compound containing a deuterated benzene ring (Compound of Formula I) to prepare an organic electroluminescent device. Among them, Examples 1 to 15 used a compound containing deuterated phenylfluorene and a triazine group.

[0306] For the structural schematic diagram of the organic electroluminescent device, see Figure 1 . The organic electroluminescent device includes a glass substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, an electron blocking layer 150, a light-emitting layer 160, a hole blocking layer 170, an electron transport layer 180, an electron injection layer 190, and a cathode 200 that are sequentially stacked.

[0307] The more detailed structure of the organic electroluminescent device in each example is: glass / anode (ITO) / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / light-emitting layer (EML, host material BH: blue light-emitting material BD) / hole blocking layer (HBL) / electron transport layer (ETL, electron transport material includes lithium 8-hydroxyquinoline (Liq or LiQ)) / electron injection layer (EIL) / cathode (Cathode).

[0308] Example 1. An OLED was prepared using Compound 1 synthesized in Preparation Example 1.

[0309] The transparent conductive ITO glass substrate 110 (with the anode 120 on it) (China Southern Glass Group Co., Ltd.) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and then sequentially washed with ethanol, acetone, and deionized water, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and then treated with oxygen plasma for 30 seconds. The above-mentioned glass substrate with the anode was placed in a vacuum chamber and evacuated.

[0310] Hole injection layer: HIL (10 nm) was evaporated on the ITO as the hole injection layer 130 at an evaporation rate of 0.1 nm / s.

[0311] Hole transport layer: Compound HT was evaporated on the hole injection layer to form a 100-nm-thick hole transport layer 140 at an evaporation rate of 0.1 nm / s.

[0312] Electron blocking layer: EB was evaporated to form a 5-nm-thick electron blocking layer 150 at an evaporation rate of 0.1 nm / s.

[0313] Light-emitting layer: A 25-nm-thick light-emitting layer 160 was evaporated on the electron blocking layer. Among them, BH was the host light-emitting material, and BD was used as the doped guest material at a weight ratio of 3%, and the evaporation rate was 0.1 nm / s.

[0314] HB-1 was evaporated on the light-emitting layer to form a 5-nm-thick hole-blocking layer 170 at an evaporation rate of 0.1 nm / s.

[0315] A 25-nm-thick compound 1 and Liq (weight ratio 5:5) were evaporated on the light-emitting layer as the electron-transporting layer 180 at an evaporation rate of 0.1 nm / s.

[0316] 1-nm-thick Liq was evaporated as the electron-injecting layer 190.

[0317] 120-nm-thick aluminum (Al) was evaporated as the device cathode 200.

[0318] 3. Examples 2-18 and Comparative Examples 1 to 6

[0319] The preparation methods of the devices in Examples 2-18 and Comparative Examples 1 to 6 were basically the same as those in Example 1, except that the electron materials used in the electron-transporting layer (ETL) and hole-blocking layer (HBL) in the devices were different. The electron materials used in each example and each comparative example are shown in Table 3.

[0320] The structures of some compounds involved in Table 3 are shown below.

[0321]

[0322] In Table 3, HIL represents the hole-injecting layer, HTL represents the hole-transporting layer, EBL represents the electron-blocking layer, EML represents the light-emitting layer, HBL represents the hole-blocking layer, ETL represents the electron-transporting layer, and EIL represents the electron-injecting layer. The percentage content ratio of the two raw materials in the EML refers to the weight ratio. For example, in Example 1, the weight ratio of BH and BD was 97%:3%. The percentage content ratio of the two raw materials in the ETL also refers to the weight ratio. For example, in Example 1, the weight ratio of compound 1 and LiQ was 50%:50%.

[0323] Table 3.

[0324]

[0325]

[0326] III. Testing and Analysis

[0327] 1. Device Performance Testing

[0328] Test Samples: Organic electroluminescent devices prepared in Examples 1-18 and Comparative Examples 1-6 of the second part.

[0329] Instruments and Methods: The performance of the devices was tested using a Photo Research PR655 spectrometer, and the measurement was carried out at 1000 cd / cm 2The operating voltage, current efficiency, emission wavelength at a certain brightness, and the time (T90) when the brightness becomes 90% of the initial brightness at a current density of 12 mA / cm 2 were measured.

[0330] The device performance parameters and test results are shown in Table 4. The test results of Examples 1-18 correspond to Test Examples 1A to 18A, and the test results of Comparative Examples 1-6 correspond to Test Comparative Examples 1A-6A.

[0331] Table 4.

[0332]

[0333]

[0334] 2. Glass transition temperature Tg (°C) of the electron transport material

[0335] Test samples: Refer to the compounds providing the electron transport material shown in Table 5.

[0336] Instruments and methods: Use a differential scanning calorimeter Pyris Diamond (DSC2920) to test the glass transition temperature (Tg) of the compound under nitrogen protection at a heating and cooling rate of 10 °C / min.

[0337] The test results are shown in Table 5 below.

[0338] Table 5.

[0339]

[0340] 3. Electron mobility of the electron transport material

[0341] To measure the electron mobility of the host material, a single electron device needs to be fabricated.

[0342] Test Example 1C. Using Compound 1 and LiQ as the electron transport material

[0343] Provide a single electron device, the structure diagram is as Figure 2 shown, including a substrate / anode, a hole injection layer, an electron transport layer, an electron injection layer, and a cathode stacked in sequence.

[0344] The manufacturing method of the single electron device is as follows:

[0345] Substrate / Anode: The glass substrate with ITO (Indium Tin Oxide)-Ag-ITO (Indium Tin Oxide) on the surface is washed twice in distilled water, ultrasonically washed in a commercial cleaning agent for 30 min, then repeatedly washed twice with distilled water and ultrasonically washed for 10 min. After washing, it is ultrasonically washed successively with ethanol, acetone, and isopropanol (each washing for 5 min), dried, then transferred to a plasma cleaner for 5 min of washing, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, then treated with oxygen plasma for 30 seconds, and then sent into the vacuum chamber of an evaporation coater to evacuate the air. Using this substrate as the anode, other functional layers are successively evaporated on it.

[0346] Hole Injection Layer: LiQ (10 nm) is evaporated on ITO as the hole injection layer, and the evaporation rate is 0.1 nm / s.

[0347] Electron Transport Layer: 50% LiQ (60 nm) of Compound 1 is evaporated on the hole injection layer as the electron transport layer, where Compound 1 is the electron transport material, the evaporation rate is 0.05 nm / s, doped with 50% by mass of lithium 8-hydroxyquinoline (LiQ), and the evaporation rate is 0.05 nm / s.

[0348] Electron Injection Layer: Yb (1 nm) is evaporated on the electron transport layer as the electron injection layer, and the evaporation rate is 0.1 nm / s.

[0349] Cathode: Ag:10% Mg (14 nm) is evaporated on the electron injection layer as the cathode, the evaporation rate of Ag is 0.09 nm / s, and the evaporation rate of Mg is 0.01 nm / s.

[0350] The device structures for testing in Test Examples 2C to 12C, 15C - 18C and Test Comparative Examples 1C to 2C are the same as those in Test Example 1C, and the manufacturing methods are basically the same as those in Test Example 1C. The main difference lies in the different materials used for the electron transport layer, and the compounds shown in Table 6 are used instead of Compound 1.

[0351] The mobilities of each electron transport material at a thickness of 60 nm are shown in Table 6 below. The mobilities in Table 6 are expressed in scientific notation.

[0352] In this application, the value aEb described in scientific notation is equivalent to a×10 b . For example, 1×10 4 can be recorded as 1E4.

[0353] Table 6.

[0354]

[0355] 4. HOMO Energy Level and LUMO Energy Level of Electron Transport Materials

[0356] Testing method: Use a photoelectron spectrometer AC-2 to measure the LUMO energy level of the material in a vacuum environment. Deposit the electron transport material (the compounds shown in Table 7) on an ITO substrate to form a thin film. The test conditions for AC-2 are 50 nW with a step of 0.05 nW. Use an ultraviolet spectrophotometer (UV) to measure the energy gap (Eg) of the material, and calculate the HOMO energy level through the LUMO energy level and Eg.

[0357] The test results are shown in Table 7 below.

[0358] Table 7.

[0359]

[0360]

[0361] 5. Analysis of test results

[0362] As can be seen from Table 5, when the deuteration number of the deuterated phenyl group increases, the glass transition temperature of the material increases accordingly, and the lifetime of the corresponding device in Table 4 also increases. This is because the substitution of deuterium can enhance the stability of the bonds within the molecule, reduce the internal vibration and resonance transfer of the molecule, lower the thermal decomposition rate of the molecule, thereby improving the thermal stability of the material and extending the lifetime of the material.

[0363] In addition, although fluorene has a planar biphenyl structure, strong molecular rigidity, large conjugation degree, and good thermal stability; however, ET-B does not contain a deuterated phenyl group and has a relatively small molecular weight, resulting in significantly poorer thermal stability of ET-B.

[0364] As can be seen from Table 7, when the deuteration number of the deuterated phenyl group increases, the HOMO and LUMO energy levels of the electron transport material shift to lower energy levels, and the triplet energy level decreases. This energy level shift may change the electron transport ability and efficiency, and the decreased triplet energy level can improve the luminescence efficiency and extend the lifetime. The lifetime of the corresponding device in Table 4 also increases accordingly.

[0365] As can be seen from Table 4, the devices prepared by using the compound of Formula I as the electron transport material in Examples 1-18 all have a low driving voltage, a high current efficiency, and a long device lifetime. Compared with Comparative Example 1 and Comparative Example 2, Examples 1-12 all have a lower driving voltage, a higher current efficiency, and a longer device lifetime; compared with Comparative Example 3, Examples 13-18 all have a lower driving voltage, a higher current efficiency, and a longer device lifetime. Among them, the working voltages of the devices prepared by using the compound of Formula I as the electron transport material in Examples 1-14 are all lower than 3.7 V, the current efficiencies are all higher than 8.5 cd / A, and the device lifetimes are all higher than 400 hours.

[0366] According to the test results of the devices in Example 1, Example 2, etc. in Table 4, it can also be seen that as the intramolecular deuteration rate of the compound of Formula I increases, that is, the number of deuterated benzene rings increases, the operating life (T90) of the device is significantly improved. Thus, it can be shown that deuteration has a positive gain effect on the life of the material. The more hydrogen atoms are replaced by deuterium, the longer the life of the device based on this material. In addition, it can be seen from Table 4 that when there are more deuterated phenyl groups and a higher deuterium substitution rate in the compound, although the operating life (T90) of the device is improved, it may increase the driving voltage of the device based on the material and reduce the current efficiency. The appropriate deuterium substitution rate can be selected according to the comprehensive performance requirements.

[0367] In Table 4, compared with Test Examples 1A - 18A of each of Examples 1 - 18, Test Comparative Examples 1A to 3A used compound ET-A or ET-B to replace the compound of Formula I as the electron transport material, resulting in an increase in voltage, a decrease in efficiency, and a shortening of life.

[0368] It can be seen from Table 5 that the compound of Formula I in each test example has a higher glass transition temperature than compounds ET-A and ET-B. This is because fluorene can effectively enhance the thermal stability of the material, increase the glass transition temperature of the compound of Formula I, and thus improve the device life.

[0369] It can be seen from Table 6 that the compound of Formula I in each test example has a faster electron mobility than compounds ET-A and ET-B. This is because the triazine group has a strong electronegativity, which can effectively improve electron transport and electron injection. The attachment of fluorene to the triazine increases the conjugated system of the whole compound. When the compound of Formula I is used as the electron transport material to prepare a thin film, it is beneficial to the intermolecular stacking, improves the charge transfer, increases the charge transport ability of the material, and can reduce the working voltage of the electronic device. In addition, the deuterium substitution present in the compound of Formula I can reduce the vibration energy level, reduce the loss, and also improve the efficiency and extend the life of the device.

[0370] In Table 4, it can be seen from Test Comparative Examples 4A and 5A that when BCP or TPBi is used to replace HB-1 as the hole blocking material, in Test Comparative Example 4A compared with Test Example 1A of Example 1, and in Test Comparative Example 5A compared with Test Example 4A of Example 4, the voltage of the device increases, the efficiency decreases, and the life shortens. According to Test Comparative Example 6A, using ET-B as the electron transport material and TPBi as the hole blocking material also results in an increase in voltage, a decrease in efficiency, and a shortening of life.

[0371] According to Table 4, for Compound 24 in Test Example 16A, no deuterated phenyl group is provided on the fluorene ring, and only a deuterated phenyl group is provided on the triazine ring. Compared with Test Examples 1A and 4A using Compound 1 and Compound 4 as the electron transport material, the device voltage of Test Example 16A increases, the efficiency decreases, and the lifetime shortens.

[0372] According to Table 4, for Compound 25 in Test Example 17A, no deuterated phenyl group is provided on the fluorene ring, and only deuterium substitution is provided in the linking group L2 connecting the fluorene ring and the triazine ring. Compared with Test Examples 1A, 4A, and 15A using Compound 1, Compound 4, and Compound 23 as the electron transport material, the device voltage of Test Example 17A increases, the efficiency decreases, and the lifetime shortens. In addition, it can be seen that the device performance of Test Example 16A is superior to that of Test Example 17A.

[0373] According to Table 4, although a deuterated phenyl group is provided on the fluorene ring in Compound 26 of Test Example 18A, L1 is not a single bond or a phenylene group, but a deuterated phenylene group. Compared with Test Example 13A using Compound 1 (L1 is a single bond) as the electron transport material, although the lifetime of the device in Test Example 18A is extended, the voltage increases and the efficiency decreases. In addition, compared with Test Example 14A using Compound 4 as the electron transport material (L1 is a phenylene group without deuteration), the device voltage of Test Example 18A increases, the efficiency decreases, and the lifetime shortens.

[0374] It can be seen that the compound of Formula I has excellent electron transport performance, and the prepared organic electroluminescent device has good optoelectronic performance in terms of driving voltage, current efficiency, and device lifetime. When the compound of Formula I is used in combination with the hole blocking material combination in Table 2 as the electron transport material, holes can be better blocked from entering the electron transport layer, and the organic electroluminescent device has better optoelectronic performance in terms of driving voltage, current efficiency, and device lifetime.

[0375] The technical features of the above embodiments and examples can be combined in any suitable manner. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments and examples are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification.

[0376] The above-described embodiments and examples merely represent several embodiments of the present application, facilitating a detailed understanding of the technical solutions of the present application. However, it should not be construed as a limitation of the protection scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can be made, and these all fall within the protection scope of the present application. In addition, it should be understood that after reading the above teachings of the present application, those skilled in the art can make various changes or modifications to the present application, and the equivalent forms obtained also fall within the protection scope of the present application. It should also be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning, or limited experiments based on the technical solutions provided by the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application shall be determined by the content of the appended claims, and the specification and drawings can be used to explain the content of the claims.

Claims

1. A fluorene-based triazine compound containing a deuterated benzene ring, characterized in that, Has the structure shown in Formula I: In Formula I, R1, R2, R3, R4, R5, R6 and R7 are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group, a tolyl group or a deuterated phenyl group; L1 is a single bond, a phenylene group or a deuterated phenylene group; L2 is a single bond, a phenylene group or a substituted phenylene group, wherein the phenylene group in the substituted phenylene group is substituted by 1, 2, 3 or 4 groups selected from the following group: a methyl group, a bromo group, a chloro group and a deuterium atom; Ar1 and Ar2 are each independently a C6-C 30 aryl, a C6-C 30 substituted aryl, a C3-C 30 heteroaryl, or a C3-C 30 substituted heteroaryl; wherein the aryl in the C6-C 30 substituted aryl and the heteroaryl in the C3-C 30 substituted heteroaryl are each independently substituted by one or more groups selected from the group consisting of a deuterium atom, a cyano group, a substituted phenyl group, and a pyridyl group, and the phenyl in the substituted phenyl group is substituted by one or more cyano groups; Wherein at least one of R1, R2, R3, R4, R5, R6, R7, L2, Ar1 and Ar2 is a deuterated benzene ring.

2. The fluorenyltriazine compound containing a deuterated benzene ring according to claim 1, characterized in that, At least one of R1, R2, R3, R4, R5, R6 and R7 is a deuterated phenyl group, and the rest are each independently a hydrogen atom, a deuterium atom, a methyl group, a phenyl group, a biphenyl group or a tolyl group; L1 is a single bond or a phenylene group.

3. The fluorenyltriazine compound containing a deuterated benzene ring according to claim 1, wherein L2 is a single bond, or L2 is a phenylene group or a deuterated phenylene group; When L2 is a phenylene group or a deuterated phenylene group, the number of deuterium atoms in the deuterated phenylene group is 1, 2, 3 or 4; the two connecting sites of L2 are ortho, meta or para positions.

4. The fluorene-based triazine compound containing a deuterated benzene ring according to claim 1, characterized in that, L2 is connected to any one of the following connecting sites:

5. The fluorene-based triazine compound containing a deuterated benzene ring according to claim 1, wherein Ar1 and Ar2 are each independently a phenyl group, a deuterated phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a benzonitrile phenyl group, a pyridyl phenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a pyridyl group or a benzonitrile group.

6. The fluorenyltriazine compound containing a deuterated benzene ring according to claim 1, characterized in that, Ar1 and Ar2 are each independently a phenyl group, a deuterated phenyl group, a benzonitrile phenyl group, a pyridyl phenyl group or a benzonitrile group; The benzonitrile group phenyl is a phenyl group substituted by ; The pyridylphenyl is a phenyl group substituted by ; The benzonitrile group is 7. The fluorenyltriazine compound containing a deuterated benzene ring according to any one of claims 1 to 6, characterized in that, Each occurrence of the deuterated phenyl group is independently any one of the groups selected from the following group:

8. The fluorenyltriazine compound containing a deuterated benzene ring according to any one of claims 1 to 6, characterized in that, Each occurrence of the deuterated phenyl group, the positions where the deuterium atoms in the deuterated phenyl group are located are selected from some or all of the para and meta positions.

9. The fluorene-based triazine compound containing a deuterated benzene ring according to any one of claims 1 to 6, characterized in that The total number of deuterated phenyl groups in R1, R2, R3, R4, R5, R6 and R7 is 1, and the structure of the deuterated phenyl group is Alternatively, the total number of deuterated phenyl groups in R1, R2, R3, R4, R5, R6 and R7 is greater than or equal to 2, and the number of deuterium atoms contained in any one of the deuterated phenyl groups is independently 1, 2, 3 or 4; The total number of deuterated phenyl groups in Ar1 and Ar2 is 1, and the structure of the deuterated phenyl group is Alternatively, the total number of deuterated phenyl groups in Ar1 and Ar2 is greater than or equal to 2, and the number of deuterium atoms contained in any one of the deuterated phenyl groups is independently 1, 2, 3, or 4.

10. The fluorene-based triazine compound containing a deuterated benzene ring according to claim 1, wherein Is any one of the following compounds:

11. An organic electronic material, characterized in that, Contains the fluorene-based triazine compound containing a deuterated benzene ring described in any one of claims 1 to 10.

12. An organic electroluminescent device, characterized in that, At least includes an anode, a cathode and an organic layer; the organic layer includes at least one structural layer of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; Wherein at least one structural layer in the organic layer contains at least one of the fluorene-based triazine compound containing a deuterated benzene ring described in any one of claims 1 to 10 and the organic electronic material described in claim 11.

13. The organic electroluminescent device according to claim 12, characterized in that, Satisfies one or more of the following characteristics: The organic layer includes at least one structural layer of the hole blocking layer and the electron transport layer, wherein at least one structural layer of the hole blocking layer and the electron transport layer contains at least one of the fluorene-based triazine compound containing a deuterated benzene ring and the organic electronic material; The organic electroluminescent device is a single electron device, and the organic layer includes at least one structural layer of the hole injection layer, the electron transport layer and the electron injection layer; The organic electroluminescent device includes the electron transport layer, and the electron transport layer contains at least one of the fluorene-based triazine compound containing a deuterated benzene ring and the organic electronic material; The hole blocking layer contains one or more of the following compounds:

14. The application of the fluorene-based triazine compound containing a deuterated benzene ring as described in any one of claims 1 to 10 or the organic electronic material as described in claim 11 includes at least the application in the preparation of an organic electroluminescent device.

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