Self-host chiral organic light-emitting compound and application thereof

Abstract

The invention relates to the technical field of display, in particular to a self-host chiral organic light-emitting compound and application thereof. The self-host chiral organic light-emitting compound provided by the invention has a structure # imgabs0 # as shown in a formula (1), and groups for limiting substituent groups and linking positions of the compound, so that the compound with the structure as shown in the formula (1) has the characteristics of high symmetry factor and good light-emitting efficiency, and can be used as a non-doped light-emitting layer material.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and in particular to a self-host chiral organic light-emitting compound and application thereof. Background Art

[0002] At present, significant progress has been made in the research of organic light-emitting diodes (OLEDs). Thermally activated delayed fluorescence (TADF) materials can convert triplet excitons into singlet excitons through reverse intergap crossing from triplet to singlet states, and then use singlet excitons to emit light, thereby theoretically achieving 100% internal quantum efficiency. Therefore, the development of thermally activated delayed fluorescence materials plays a key role in improving the efficiency of organic electroluminescent devices, and can avoid the use of phosphorescent materials containing precious metals, which is also of positive significance for promoting commercial applications. Since 2001, the concept of "aggregation-induced emission (AIE)" has been proposed. When molecules aggregate, the luminescence intensity of the molecules increases significantly. Based on this type of material, non-doped OLEDs with simple device structures have been developed, but this type of material can only use singlet excitons to emit light, and the device efficiency is low.

[0003] In recent years, chiral materials with circularly polarized luminescence (CPL) properties have attracted much attention in the fields of data storage, photonic technology, display and biosensing. Usually, a quarter-wave plate is used in the application process, resulting in at least 50% luminosity loss and process complexity. Circularly polarized organic light-emitting diodes (CP-OLEDs) can directly generate circularly polarized light, avoiding brightness drop and efficiency loss, and have high application potential in three-dimensional displays.

[0004] Although existing chiral TADF materials can also achieve high efficiency and circularly polarized luminescence characteristics at the same time, most luminescent materials have obvious aggregation-induced fluorescence quenching, so they need to be dispersed in the host material to reduce the quenching effect, and the introduction of the host material will increase the complexity and cost of the preparation process. Therefore, there is an urgent need in the relevant technology for a compound with a high symmetry factor, good luminescence efficiency and that can be used as a non-doped luminescent layer material. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem in the related art that there is a lack of a compound with a high symmetry factor, good luminescence efficiency and can be used as a non-doped luminescent layer material, and further to provide a self-host chiral organic luminescent compound and its application.

[0006] The term "substituent" in this disclosure has its ordinary meaning as known in the art and refers to a chemical moiety that is covalently attached or, where appropriate, fused to a parent core group.

[0007] In the present application, the term "substituted or unsubstituted" means that the functional group recorded after the term may or may not have a substituent (hereinafter, for ease of description, the substituent is collectively referred to as Rc). For example, "substituted or unsubstituted aryl" refers to an aryl or non-substituted aryl having a substituent Rc. Wherein the above-mentioned substituent, i.e., Rc, can be, for example, deuterium, halogen, cyano, C1-C60 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C1-C60 heteroaryl, and optionally, for example, deuterium, halogen group, cyano, alkyl, haloalkyl, trialkylsilyl, deuterated alkyl, aryl, heteroaryl, etc. Of course, the number of substituents Rc can be one or more. When two substituents Rc are connected to the same atom, the two substituents Rc can exist independently or be connected to each other to form a ring with the atom; when two adjacent substituents Rc exist on a functional group, the adjacent substituents Rc can exist independently or be fused to form a ring with the functional group to which they are connected.

[0008] In the present application, the term "alkyl" refers to a saturated hydrocarbon group, whether used as part of other terms or alone, which can be straight or branched. The term "C1-C60 alkyl" is derived from a monovalent substituent of a straight or branched saturated hydrocarbon having 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms, of course, examples thereof include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0009] In the present application, the term "C3-C60 cycloalkyl" refers to a ring alkyl group consisting of at least 3 atoms, and further refers to a cycloalkyl group derived from a monocyclic hydrocarbon or polycyclic hydrocarbon having 3 to 60 ring main chain carbon atoms, preferably 3 to 40 carbon atoms, and more preferably 3 to 20 carbon atoms. Of course, the cycloalkyl group includes but is not limited to cyclopropyl, cyclobutyl, adamantyl, etc.

[0010] In the present application, the terms "aryl" and "arylene" include monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0011] In the present application, the term "heteroaryl" includes monocyclic, polycyclic or condensed-ring heteroaryl groups, wherein the rings may be interrupted by short non-aromatic units, wherein the heteroatoms include nitrogen, oxygen, and sulfur, and the heteroaryl groups in the present application include but are not limited to furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimid ... pyridyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl , and derivatives thereof; heteroarylene groups include, but are not limited to, furanylene, phenylthioene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazolylene, pyridinylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, Furanyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof. As used in the present invention, the term "substituted" refers to a hydrogen atom in a compound that is replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0012] In the present application, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine and iodine.

[0013] In the present application, unless otherwise specified, a hydrogen atom includes protium, deuterium and tritium.

[0014] In the present application, the range of carbon atom number is defined in the definition of the group, and the carbon atom number is any integer within the defined range. For example, C6-C60 aromatic group, the carbon atom number representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0015] In the present application, if a group is not limited to being substituted or unsubstituted, it means being unsubstituted.

[0016] The scheme adopted by the present invention is as follows:

[0017] The present invention provides a self-host chiral organic light-emitting compound having the following structure:

[0018]

[0019] wherein X is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)- or -(C=O)-;

[0020] Y is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)-, -(C=O)-,

[0021] Ar1 is selected from a substituted or unsubstituted C5-C80 aryl ring, or a substituted or unsubstituted C3-C80 aryl heterocycle;

[0022] When Y is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)- or -(C=O)-, Ar2 is absent;

[0023] When Y is selected from When Ar2 is present, it is selected from a substituted or unsubstituted C5-C80 aryl ring, or a substituted or unsubstituted C3-C80 aryl heterocycle;

[0024] The substituents in the substituted C5-C80 aryl ring and the substituted C3-C80 aryl heterocyclic ring are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl; the heteroatoms in the heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0025] R, R ’ Respectively represent Ar and Ar ’ Substituents on ’ Each is independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl;

[0026] n、n ’ Ar, Ar ’ The number of substituents on

[0027] Ar, Ar ’ Can exist independently or linked.

[0028] In the present invention, the dashed line may or may not exist; for example: It means that when Y is -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)-, -(C=O)-, it does not exist; R ’ Doesn't exist either.

[0029] In the present invention, the substituted or unsubstituted C5-C80 aryl ring includes C10, C15, C20, C30, C40, C50;

[0030] The substituted or unsubstituted C3-C80 aromatic heterocycle includes C10, C15, C20, C30, C40, and C50.

[0031] An aryl ring may also be referred to as an aromatic ring in other fields; an aryl heterocyclic ring may also be referred to as a heteroaromatic ring in other fields.

[0032] Preferably, the self-host chiral organic light-emitting compound has a structure shown in the following formula-1-1 or formula-1-2:

[0033]

[0034] Wherein, X and X1 are independently selected from -O-, -S-, -Se-, -Te-;

[0035] Y is selected from

[0036] Ar1 and Ar2 are each independently selected from a substituted or unsubstituted C5-C60 aryl ring, or a substituted or unsubstituted C3-C60 aryl heterocycle;

[0037] The substituents in the substituted C5-C60 aryl ring and the substituted C3-C60 aryl heterocyclic ring are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl; the heteroatoms in the substituted C3-C60 aryl heterocyclic ring and C3-C60 heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0038] R1, R2, and R3 represent substituents on Ar1, Ar2, and Ar3, respectively; R1, R2, and R3 are independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl;

[0039] n1, n2, n3 represent the number of substituents on Ar1, Ar2, Ar3, and n1, n2, n3 are each independently selected from integers of 0 to 5;

[0040] In Formula 1-2, Ar1, Ar2, and Ar3 exist independently or in combination.

[0041] Optionally, n1, n2, n3 are each independently selected from 0, 1, 2, 3, 4 or 5.

[0042] In the present invention, the substituted or unsubstituted C5-C60 aryl ring includes C10, C15, C20, C30, C40, C50;

[0043] The substituted or unsubstituted C3-C60 aromatic heterocycle includes C10, C15, C20, C30, C40, and C50.

[0044] Preferably, in Formula 1-2, Ar1 and Ar3 are connected by a single bond, -C(L1L2)-, -(C=O)-, -N(L1)-, -O-, -S-, -Se-, -Te-, -S(O2)- or Link;

[0045] The L1-L2 are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se;

[0046] The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl;

[0047] Preferably, in Formula 1-2, Ar2 and Ar3 are connected by single bonds, -C(L1L2)-, -(C=O)-, -N(L1)-, -O-, -S-, -Se-, -Te-, -S(O2)-, Link;

[0048] The L1-L2 are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se;

[0049] The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

[0050] Taking -C(L1L2)- as an example, “-” represents a connecting bond.

[0051] Preferably, in Formula-1-1, the carbon atoms on Ar1 and Ar2 form a five-membered ring or a six-membered ring through their respective connected Y and X1;

[0052] Preferably, in formula-1-2, the carbon atoms on Ar1 and Ar2 form a six-membered ring through their respective connected Y and N;

[0053] Preferably, in formula-1-2, the carbon atoms on Ar1 and Ar3 form a five-membered ring or a six-membered ring through their respective connected N;

[0054] Preferably, in formula-1-2, the carbon atoms on Ar2 and Ar3 form a five-membered ring or a six-membered ring through their respective connected N;

[0055] Preferably, the carbon atom on Ar1 preferentially forms a six-membered ring through the carbon atoms of the chiral biphenyl ring connected thereto, X and Y;

[0056] Preferably, Ar1, Ar2, and Ar3 are each independently selected from one of the following rings:

[0057]

[0058] Wherein, each of L1 to L2 is independently selected from substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 alkylthio, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3 to C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se;

[0059] The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

[0060] It can be understood that, in the above ring, there may be two, three or four connection sites to connect with the surrounding groups to be connected; taking Formula-1-1 as an example, if Ar1 is , point 1 is connected to X, point 2 is connected to Y, and point 3 is connected to X1.

[0061] Preferably, the self-host chiral organic light-emitting compound has a structure shown in the following formula-1-3 or formula-1-4:

[0062]

[0063] X3, X4 are independently selected from -C(H2)-, -S(O2)-, -O- or -(C=O)-;

[0064] Ar4 is an electron donating group selected from substituted or unsubstituted C3-C60 heteroaryl groups; the substituents in the substituted C3-C60 heteroaryl groups are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl groups; the heteroatoms in the C3-C60 heteroaryl groups and the substituted or unsubstituted C3-C60 aromatic heterocycles are selected from one or more of Si, Ge, N, P, O, S and Se.

[0065] Preferably, Ar4 is independently selected from one of the following groups:

[0066]

[0067] Wherein, each of L1 to L2 is independently selected from H, D, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 alkylthio, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3 to C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se;

[0068] The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

[0069] Indicates a connection key.

[0070] Preferably, the structure of the self-host chiral organic light-emitting compound is selected from any one of the following structures:

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] Wherein, R1-R4 are each independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl;

[0080] n1 to n4 are the numbers of R1 to R4, respectively, and n1 to n4 are each independently selected from integers of 0 to 5;

[0081] The L1-L2 are each independently selected from H, D, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se;

[0082] The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

[0083] Preferably, n1-n4 are 0; L1-L2 are methyl groups.

[0084] The present invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer located between the anode and the cathode, wherein the organic layer comprises the self-host chiral organic light-emitting compound as described above.

[0085] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the self-host chiral organic light-emitting compound as described above.

[0086] The present invention also provides an electronic device, which includes the organic electroluminescent device as described above.

[0087] Beneficial effects of the present invention:

[0088] The self-host chiral organic light-emitting compound provided by the present invention has a structure shown in formula (1), wherein the mother core uses octahydrobinaphthyl as the chiral axis, a diphenylphosphine oxide group with steric hindrance is introduced on one side, and an aromatic condensed ring is introduced on the other side as a light-emitting unit, and the charge transfer effect of the condensed ring unit or the donor-acceptor structure is utilized to achieve a smaller single-triplet energy difference (ΔEST) and TADF effect, and the self-carried diphenylphosphine oxide unit can play a part of the host role, thereby making the compound with the structure of formula (1) have the characteristics of high symmetry factor and good luminescence efficiency, and can be used as a non-doped light-emitting layer material.

[0089] Furthermore, the self-host chiral organic light-emitting compound provided by the present invention has simple synthesis steps, is easy to separate chirally, and has the advantage of low cost, so it can be better applied. BRIEF DESCRIPTION OF THE DRAWINGS

[0090] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0091] Figure 1 The ultraviolet absorption spectrum and fluorescence spectrum of the compound S-II-52 obtained in Example 8 of the present invention in toluene solution;

[0092] Figure 2 The ultraviolet absorption spectrum and fluorescence spectrum of the compound S-III-56 obtained in Example 13 of the present invention in a toluene solution at room temperature;

[0093] Figure 3 The fluorescence spectra of compound S-III-56 obtained in Example 13 in mixed solvents of water / tetrahydrofuran at different ratios;

[0094] Figure 4 The transient fluorescence lifetime spectrum of compound S-III-7 obtained in Example 12;

[0095] Figure 5 This is the photoinduced circularly polarized luminescence spectrum of compound S-III-7 obtained in Example 12. DETAILED DESCRIPTION

[0096] The following examples are provided for a better understanding of the present invention, and are not limited to the best embodiment, and do not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the enlightenment of the present invention or by combining the features of the present invention with other prior arts falls within the protection scope of the present invention. For example, the synthesis of the non-exemplified compounds according to the present application can be successfully completed by a person skilled in the art through modification methods, such as appropriate protection of interfering groups, by using other known reagents in addition to those described in the present application, or making some conventional modifications to the reaction conditions, all of which fall within the protection scope of the present invention.

[0097] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0098] The specific structure of the raw materials used in the embodiments of the present invention is as follows:

[0099] Preparation of intermediate R / S-3

[0100] The specific steps of intermediate R / S-3 are:

[0101]

[0102] Under argon atmosphere, R / S-5,5',6,6',7,7',8,8'-octahydro-1,1'-di-2-naphthol (2.0 g, 6.8 mmol) was added to a 250 mL three-necked flask, and 60 mL of dichloromethane was added, and pyridine (1.4 mL, 17.6 mmol) was added to the solution. Stir at room temperature for 5 minutes, and trifluoromethanesulfonic anhydride (2.5 mL, 14.9 mmol) was slowly added dropwise at 0°C, and stirred at room temperature for 12 hours. After the reaction was completed, the solvent in the reaction system was dried, and the obtained solid was separated by silica gel column to obtain intermediate R / S-1 (3.6 g, yield: 95%).

[0103] Under argon atmosphere, add intermediate R / S-1 (2.3g, 4.1mmol), diphenylphosphine oxide (1.7g, 8.3mmol), palladium acetate (92.5mg, 0.4mmol), 1,4-bis(diphenylphosphine)butane (175.7mg, 0.4mmol), and dimethyl sulfoxide (23mL) to a 100mL bottle. Then slowly add N,N-diisopropylethylamine (2.9mL, 16.5mmol), stir the reaction system at room temperature for 20 minutes, and then heat to 110℃ for 12 hours. After the reaction is completed, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-2 (2.2g, yield: 88%).

[0104] Under argon atmosphere, add intermediate R / S-2 to a 100mL three-necked flask, dissolve it with a mixed solvent (30mL) of 1,4-dioxane / methanol (volume ratio 2:1), add sodium hydroxide aqueous solution (10mL, 3mol / L) at 0℃, and stir the reaction system at room temperature for 12 hours. After the reaction, cool the reaction system to 0℃, slowly add concentrated hydrochloric acid (about 2.5mL) to adjust the pH to 3. Remove the organic solvent by vacuum distillation, dilute the residue with ethyl acetate, wash with brine, and dry over anhydrous sodium sulfate. The organic phase is spin-dried to obtain an off-white solid R / S-3.

[0105] Example 1

[0106] This embodiment provides compound R / SI-1, whose structural formula and synthesis route are as follows:

[0107]

[0108] The specific implementation steps are:

[0109] Under argon atmosphere, 1-bromo-2,6-difluorobenzene (compound 1-1) (15.4 g, 80.0 mmol), thiophenol (8.8 g, 80.0 mmol), potassium carbonate (22.1 g, 160.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N-methylpyrrolidone was added, and the temperature was raised to 120°C for 6 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound 1-2 (10.1 g, yield: 45%).

[0110] Under argon atmosphere, compound 1-2 (6.2 g, 22.0 mmol), R / S-3 (9.6 g, 20.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 110°C for reaction for 8 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-4 (12.3 g, yield: 83%).

[0111] Under argon atmosphere, R / S-4 (7.4 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for reaction for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for reaction for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / SI-1 (2.1 g, yield: 31%) was obtained by silica gel column separation. C44H36BO2PS; M / Z = 670.23, theoretical value 670.23 (100%), 671.23 (44.8%), 669.23 (22.2%), 672.23 (11.1%), 672.22 (4.0%), 671.24 (2.5%), 673.23 (2.3%), 673.24 (1.6%); Elemental analysis: C, 78.81; H, 5.41; B, 1.61; O, 4.77; P, 4.62; S, 4.78.

[0112] Example 2

[0113] This example provides compound R / SI-31, whose structural formula and synthesis route are as follows:

[0114]

[0115] The specific implementation steps are:

[0116] Under argon atmosphere, 3-bromo-2,4-difluoro-9,9-dimethylfluorene (compound 2-1) (24.6 g, 80.0 mmol), phenylselenol (12.6 g, 80.0 mmol), potassium carbonate (22.1 g, 160.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N-methylpyrrolidone was added, and the temperature was raised to 120 ° C for 6 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound 2-2 (15.0 g, yield: 42%).

[0117] Under argon atmosphere, compound 2-2 (9.8 g, 22.0 mmol), R / S-3 (9.5 g, 20.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 115 ° C for 5 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-5 (7.2 g, yield: 79%).

[0118] Under argon atmosphere, R / S-5 (9.0 g, 10.00 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for reaction for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for reaction for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / SI-31 (1.7 g, yield: 20%) was obtained by silica gel column separation. C53H44BO2PSe; M / Z = 834.22, theoretical value 834.23 (100%), 835.24 (67.9%), 833.24 (57.2%), 831.24 (40.3%), 830.24 (25.3%), 834.24 (22.5%), 836.23 (17.6%), 837.24 (14.1%), 829.24 (5.7%), 828.24 (1.8%), 836.25 (1.0%), 834.25 (1.0%); Elemental analysis: C, 76.36; H, 5.32; B, 1.30; O, 3.84; P, 3.72; Se, 9.47.

[0119] Example 3

[0120] This example provides compound R / SI-43, whose structural formula and synthesis route are as follows:

[0121]

[0122] The specific implementation steps are:

[0123] Under argon atmosphere, 2-bromo-3-chlorobenzenethiol (compound 3-1) (16.5 g, 80.0 mmol), thiophene-2-selenol (17.1 g, 80.0 mmol), potassium carbonate (22.1 g, 160.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N-methylpyrrolidone was added, and the temperature was raised to 120°C for 6 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound 3-2 (14.1 g, yield: 44%).

[0124] Under argon atmosphere, compound 3-2 (16.5 g, 22.0 mmol), R / S-2 (12.2 g, 20.0 mmol), cuprous iodide (190.5 mg, 1.0 mmol), ethylene glycol (2.5 g, 40.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, 100 mL of isopropanol was added, and the temperature was raised to 80 ° C for 24 hours. After the reaction was completed, the solvent in the reaction system was dried, extracted three times with dichloromethane and water, and the organic phase was taken. Dichloromethane was removed by vacuum distillation, and the intermediate R / S-6 (12.1 g, yield: 70%) was obtained by silica gel column separation.

[0125] Under argon atmosphere, R / S-6 (8.7 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for reaction for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for reaction for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by distillation under reduced pressure. Compound R / SI-43 (1.7 g, yield: 21%) was obtained by silica gel column separation. C42H34BOPS2Te; M / Z = 790.09, theoretical value 790.09 (100%), 788.09 (91.8%), 789.10 (65.5%), 791.10 (46.3%), 787.09 (27.3%), 790.10 (21.5%), 788.10 (15.8%), 792.09 (8.4%), 791.09 (7.3%), 793.09 (4.0%), 793.10 (2.0%), 782.10 (1.4%); Elemental analysis: C, 64.00; H, 4.35; B, 1.37; O, 2.03; P, 3.93; S, 8.13; Te, 16.19.

[0126] Example 4

[0127] This example provides compound R / SI-53, whose structural formula and synthesis route are as follows:

[0128]

[0129] The specific implementation steps are:

[0130] Under argon atmosphere, 1-bromo-2,6-difluorobenzene (compound 1-1) (15.4 g, 80.0 mmol), dibenzothiophene-2-selenol (21.1 g, 80.0 mmol), potassium carbonate (22.1 g, 160.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N-methylpyrrolidone was added, and the temperature was raised to 120 ° C for 6 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound 4-1 (19.3 g, yield: 45%).

[0131] Under argon atmosphere, compound 4-1 (9.6 g, 22.0 mmol), R / S-3 (9.6 g, 20.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 110 ° C for 5 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-7 (14.3 g, yield: 80%).

[0132] Under argon atmosphere, add R / S-7 (8.9 g, 10.0 mmol) to a 150 mL pressure bottle and add 60 mL toluene to dissolve. Add n-butyl lithium solution in n-pentane solution (4.8 mL, 2.5 M, 12.0 mmol) dropwise at 0°C, heat to 70°C and react for 4 hours. Cool to 0°C, add phosphorus trichloride (0.7 mg, 5.0 mmol), heat to 80°C and react for 1 hour. Add sulfur (0.6 g, 18.0 mmol) and continue stirring for 1 hour. Cool the reaction system to 0°C again and add aluminum chloride (1.0 g, 7.5 mmol) and N,N-diisopropylethylamine (2.6 mL, 16.0 mmol), slowly heat to room temperature and seal, continue to heat to 80°C and stir for 20 hours. After cooling to room temperature, the reaction system was poured into 1,4-diazabicyclo[2.2.2]octane (15.7 g, 14.0 mmol) in dichloromethane (100 mL), filtered with suction using diatomaceous earth, and the organic solvent was removed by distillation under reduced pressure. The intermediate R / S-8 (3.5 g, yield: 40%) was obtained by separation on a silica gel column.

[0133] Under air atmosphere, R / S-8 (8.8 g, 10.0 mmol) and m-chloroperbenzoic acid (2.2 g, 77 w%, 10.0 mmol) were added to a 150 mL three-necked flask, and 100 mL of dichloromethane was added to dissolve, and stirred at room temperature for 22 hours. Cooled to 0°C, m-chloroperbenzoic acid (0.7 g, 77 w%, 3.0 mmol) was added, and stirred at room temperature for 1 hour. Saturated sodium sulfite aqueous solution was added and stirred at room temperature, insoluble matter was filtered off, and the liquid was separated to take the organic layer. The solvent was removed by reduced pressure distillation, and compound R / SI-53 (5.6 g, yield: 65%) was obtained by silica gel column separation. C50H38O3P2SSe; M / Z = 860.12, theoretical value 860.12 (100%), 858.12 (56.7%), 861.12 (56.2%), 859.12 (27.3%), 863.12 (12.3%), 860.13 (7.5%), 859.13 (3.1%), 860.11 (2.1%), 854.12 (1.8%), 861.13 (1.5%); Elemental analysis: C, 69.85; H, 4.45; O, 5.58; P, 7.20; S, 3.73; Se, 9.18.

[0134] Example 5

[0135] This example provides compound R / SI-60, whose structural formula and synthesis route are as follows:

[0136]

[0137] The specific implementation steps are:

[0138] Under argon atmosphere, 4-fluoro-3-bromo-dibenzofuran-2-selenol (compound 5-1) (27.5 g, 80.0 mmol), benzotellurol (16.6 g, 80.0 mmol), potassium carbonate (22.1 g, 160.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N-methylpyrrolidone was added, and the temperature was raised to 120°C for 6 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound 5-2 (18.7 g, yield: 44%).

[0139] Under argon atmosphere, compound 5-2 (11.7 g, 22.0 mmol), R / S-2 (12.2 g, 20.0 mmol), cuprous iodide (190.5 mg, 1.0 mmol), ethylene glycol (2.5 g, 40.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, 100 mL of isopropanol was added, and the temperature was raised to 80 ° C for 24 hours. After the reaction was completed, the solvent in the reaction system was dried, extracted with dichloromethane and water three times, and the organic phase was taken. Dichloromethane was removed by vacuum distillation, and the intermediate R / S-9 (9.8 g, yield: 52%) was obtained by silica gel column separation.

[0140] Under argon atmosphere, add R / S-9 (9.4g, 10.0mmol) to a 150mL pressure bottle and add 60mL toluene to dissolve. Add n-butyl lithium solution in n-pentane solution (4.8mL, 2.5M, 12.0mmol) dropwise at 0℃, heat to 70℃ and react for 4 hours. Cool to 0℃, add phosphorus trichloride (0.7mg, 5.0mmol), heat to 80℃ and react for 1 hour. Add sulfur (0.6g, 18.0mmol) and continue stirring for 1 hour. Cool the reaction system to 0℃ again and add aluminum chloride (1.0g, 7.5mmol) and N,N-diisopropylethylamine (2.6mL, 16.0mmol), slowly heat to room temperature and seal, continue to heat to 80℃ and stir for 20 hours. After cooling to room temperature, the reaction system was poured into 1,4-diazabicyclo[2.2.2]octane (15.7 g, 14.0 mmol) in dichloromethane (100 mL), filtered with suction using diatomaceous earth, and the organic solvent was removed by distillation under reduced pressure. The intermediate R / S-10 (3.9 g, yield: 42%) was obtained by separation on a silica gel column.

[0141] Under air atmosphere, R / S-10 (9.3 g, 10.0 mmol) and m-chloroperbenzoic acid (2.2 g, 77 w%, 10.0 mmol) were added to a 150 mL three-necked flask, and 100 mL of dichloromethane was added to dissolve, and stirred at room temperature for 22 hours. Cooled to 0°C, m-chloroperbenzoic acid (0.7 g, 77 w%, 3.0 mmol) was added, and stirred at room temperature for 1 hour. Saturated sodium sulfite aqueous solution was added and stirred at room temperature, insoluble matter was filtered off, and the liquid was separated to take the organic layer. The solvent was removed by reduced pressure distillation, and compound R / SI-60 (5.8 g, yield: 64%) was obtained by silica gel column separation. C50H38O3P2SteM / Z=910.10, theoretical value 910.11 (100%), 908.11 (89.3%), 911.11 (50.7%), 906.10 (48.7%), 909.11 (45.3%), 912.11 (14.0%), 904.10 (12.4%), 913.12 (2.6%), 904.11 (2.3%), 911.12 (2.1%); elemental analysis: C, 66.11; H, 4.22; O, 5.28; P, 6.82; S, 3.53; Te, 14.05.

[0142] Example 6

[0143] This example provides compound R / S-II-2, whose structural formula and synthesis route are as follows:

[0144]

[0145] The specific implementation steps are:

[0146] Under argon atmosphere, 4-bromo-3-chloro-2-fluoro-9,9-dimethylfluorene (compound 6-1) (7.1 g, 22.0 mmol), R / S-3 (9.6 g, 20.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 110°C for 5 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-11 (11.7 g, yield: 80%).

[0147] Under argon atmosphere, add intermediate R / S-11 (7.3g, 10.0mmol), diphenylamine (2.0g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL) in a 100mL bottle. Heat to 110℃ and react for 4 hours. After the reaction is completed, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-12 (7.7g, yield: 87%).

[0148] Under argon atmosphere, R / S-12 (8.7 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / S-II-2 (3.4 g, yield: 40%) was obtained by silica gel column separation. C59H49BNO2P; M / Z = 845.36, theoretical value 845.36 (100%), 846.36 (64.3%), 844.36 (24.8%), 847.37 (21.5%), 845.37 (16.0%), 846.37 (5.7%), 848.37 (4.5%); Elemental analysis: C, 83.78; H, 5.84; B, 1.28; N, 1.66; O, 3.78; P, 3.66.

[0149] Example 7

[0150] This example provides compound R / S-II-20, whose structural formula and synthesis route are as follows:

[0151]

[0152] The specific implementation steps are:

[0153] Under argon atmosphere, 2-chloro-3-fluorobromobenzene (compound 7-1) (4.6 g, 22.0 mmol), R / S-3 (9.6 g, 20.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 110°C for 5 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-13 (11.7 g, yield: 80%).

[0154] Under argon atmosphere, add intermediate R / S-13 (6.7g, 10.0mmol), pheneselenazine (3.0g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL) in a 100mL side-mouth bottle. Heat to 110℃ and react for 4 hours. After the reaction is completed, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-14 (7.3g, yield: 87%).

[0155] Under argon atmosphere, R / S-14 (8.3 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / S-II-20 (2.9 g, yield: 36%) was obtained by silica gel column separation. C50H39BNO2PSe; M / Z = 807.20, theoretical value 807.20 (100%), 808.20 (51.9%), 805.20 (49.6%), 806.20 (45.0%), 804.20 (33.0%), 810.20 (8.5%), 807.21 (7.0%), 806.21 (4.2%), 811.20 (2.3%), 809.21 (1.1%); Elemental analysis: C, 74.45; H, 4.87; B, 1.34; N, 1.74; O, 3.97; P, 3.84; Se, 9.79.

[0156] Example 8

[0157] This example provides compound R / S-II-52, whose structural formula and synthesis route are as follows:

[0158]

[0159] The specific implementation steps are:

[0160] Under argon atmosphere, 2-chloro-3-bromobenzenethiol (compound 8-1) (4.9 g, 22.0 mmol), R / S-2 (12.2 g, 20.0 mmol), cuprous iodide (190.5 mg, 1.0 mmol), ethylene glycol (2.5 g, 40.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, 100 mL of isopropanol was added, and the temperature was raised to 80°C for 24 hours. After the reaction was completed, the solvent in the reaction system was dried, extracted three times with dichloromethane and water, and the organic phase was taken. Dichloromethane was removed by vacuum distillation, and the intermediate R / S-15 (9.8 g, yield: 72%) was obtained by silica gel column separation.

[0161] Under argon atmosphere, add intermediate R / S-15 (6.8g, 10.0mmol), 5-phenyl-5,11-dihydroindole [3,2-B] carbazole (4.0g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL) into a 100mL bottle. Heat to 110℃ and react for 4 hours. After the reaction, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-16 (8.1g, yield: 87%).

[0162] Under argon atmosphere, R / S-16 (9.3 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / S-II-52 (2.5 g, yield: 28%) was obtained by silica gel column separation. C62H46BN2OPS; M / Z = 908.32, theoretical value 908.32 (100%), 909.32 (59.7%), 907.32 (21.2%), 910.32 (20.7%), 909.33 (4.8%), 911.33 (4.4%), 910.31 (3.9%), 911.32 (3.2%), 910.33 (1.4%); Elemental analysis: C, 81.93; H, 5.10; B, 1.19; N, 3.08; O, 1.76; P, 3.41; S, 3.53.

[0163] Example 9

[0164] This example provides compound R / S-II-69, whose structural formula and synthesis route are as follows:

[0165]

[0166] The specific implementation steps are:

[0167] Under argon atmosphere, 2-chloro-3-bromobenzeneselenol (compound 9-1) (5.9 g, 22.0 mmol), R / S-2 (12.2 g, 20.0 mmol), cuprous iodide (190.4 mg, 1.0 mmol), ethylene glycol (2.5 g, 40.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, 100 mL of isopropanol was added, and the temperature was raised to 80°C for 24 hours. After the reaction was completed, the solvent in the reaction system was dried, extracted three times with dichloromethane and water, and the organic phase was taken. Dichloromethane was removed by vacuum distillation, and the intermediate R / S-17 (10.1 g, yield: 69%) was obtained by silica gel column separation.

[0168] Under argon atmosphere, add intermediate R / S-17 (7.3g, 10.0mmol), diphenylamine (2.0g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL) into a 100mL bottle. Heat to 110℃ and react for 4 hours. After the reaction, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-18 (7.2g, yield: 88%).

[0169] Under argon atmosphere, R / S-18 (8.2 g, 10.0 mmol) was added to a 150 mL pressure bottle, and 60 mL of o-dichlorobenzene was added to dissolve. A solution of n-butyl lithium in n-pentane (4.8 mL, 2.5 M, 12.0 mmol) was added dropwise at 0 ° C, and the temperature was raised to 60 ° C for 2 hours. Cooled to -40 ° C, boron tribromide (2.0 mL, 20.0 mmol) was added, and after the addition was complete, the temperature was raised to room temperature for 1 hour. The reaction system was cooled to 0 ° C again and N, N-diisopropylethylamine (3.3 mL, 20.0 mmol) was added, and the temperature was slowly raised to room temperature and sealed, and the temperature was continued to rise to 180 ° C and stirred for 24 hours. After cooling to room temperature, ethanol was added dropwise to quench, and the organic solvent was removed by vacuum distillation. Compound R / S-II-69 (2.9 g, yield: 37%) was obtained by silica gel column separation. C50H41BNOPSe; M / Z = 793.21, theoretical value 793.22 (100%), 794.22 (59.2%), 792.22 (50.9%), 791.22 (47.9%), 795.23 (17.8%), 796.22 (9.7%), 797.23 (3.0%), 790.23 (2.9%), 787.22 (1.8%), 788.23 (1.0%); elemental analysis: C, 75.77; H, 5.21; B, 1.36; N, 1.77; O, 2.02; P, 3.91; Se, 9.96.

[0170] Example 10

[0171] This example provides compound R / S-II-85, whose structural formula and synthesis route are as follows:

[0172]

[0173] The specific implementation steps are:

[0174] Under argon atmosphere, add intermediate R / S-15 (6.8g, 10.0mmol), 3,6-(diphenylamino)carbazole (6.1g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1mmol), sodium tert-butoxide (1.9g, 20mmol) and toluene (60mL) into a 100mL bottle. Heat to 110℃ and react for 4 hours. After the reaction, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-19 (9.4g, yield: 85%).

[0175] Under argon atmosphere, add R / S-19 (11.0 g, 10.0 mmol) to a 150 mL pressure bottle and add 60 mL toluene to dissolve. Add n-butyl lithium solution in n-pentane solution (4.8 mL, 2.5 M, 12.0 mmol) dropwise at 0°C, heat to 70°C and react for 4 hours. Cool to 0°C, add phosphorus trichloride (0.7 mg, 5.0 mmol), heat to 80°C and react for 1 hour. Add sulfur (0.6 g, 18.0 mmol) and continue stirring for 1 hour. Cool the reaction system to 0°C again and add aluminum chloride (1.0 g, 7.5 mmol) and N,N-diisopropylethylamine (2.6 mL, 16.0 mmol), slowly heat to room temperature and seal, continue to heat to 80°C and stir for 20 hours. After cooling to room temperature, the reaction system was poured into 1,4-diazabicyclo[2.2.2]octane (15.7 g, 14.0 mmol) in dichloromethane (100 mL), filtered with suction using diatomaceous earth, and the organic solvent was removed by distillation under reduced pressure. The intermediate R / S-20 (4.5 g, yield: 40%) was obtained by separation on a silica gel column.

[0176] Under air atmosphere, R / S-20 (11.3 g, 10.0 mmol) and m-chloroperbenzoic acid (2.2 g, 77 w%, 10.0 mmol) were added to a 150 mL three-necked flask, and 100 mL of dichloromethane was added to dissolve, and stirred at room temperature for 22 hours. Cooled to 0°C, m-chloroperbenzoic acid (0.7 g, 77 w%, 3.0 mmol) was added, and stirred at room temperature for 1 hour. Saturated sodium sulfite aqueous solution was added and stirred at room temperature, insoluble matter was filtered off, and the liquid was separated to take the organic layer. The solvent was removed by reduced pressure distillation, and compound R / SI-85 (6.8 g, yield: 61%) was obtained by silica gel column separation. C74H57N3O2P2S; M / Z = 1113.36, theoretical value 1113.36 (100%), 1114.37 (80.8%), 1115.37 (34.1%), 1116.37 (9.2%), 1115.36 (4.5%), 1116.36 (3.7%), 1114.36 (1.9%), 1117.38 (1.8%), 1117.37 (1.6%); Elemental analysis: C, 79.76; H, 5.16; N, 3.77; O, 2.87; P, 5.56; S, 2.88.

[0177] Embodiment 11

[0178] This example provides compound R / S-II-113, whose structural formula and synthesis route are as follows:

[0179]

[0180] The specific implementation steps are:

[0181] Under argon atmosphere, add intermediate R / S-17 (7.3g, 10.0mmol), 10H-spiro[aza-9,9'-fluorene] (4.0g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL) into a 100mL branched bottle. Heat to 110℃ and react for 4 hours. After the reaction is completed, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain intermediate R / S-21 (7.9g, yield: 81%).

[0182] Under argon atmosphere, add R / S-21 (9.8g, 10.0mmol) to a 150mL pressure bottle and add 60mL toluene to dissolve. Add n-butyl lithium solution in n-pentane solution (4.8mL, 2.5M, 12.0mmol) dropwise at 0℃, heat to 70℃ and react for 4 hours. Cool to 0℃, add phosphorus trichloride (0.7mg, 5.0mmol), heat to 80℃ and react for 1 hour. Add sulfur (0.6g, 18.0mmol) and continue stirring for 1 hour. Cool the reaction system to 0℃ again and add aluminum chloride (1.0g, 7.5mmol) and N,N-diisopropylethylamine (2.6mL, 16.0mmol), slowly heat to room temperature and seal, continue to heat to 80℃ and stir for 20 hours. After cooling to room temperature, the reaction system was poured into 1,4-diazabicyclo[2.2.2]octane (15.7 g, 14.0 mmol) in dichloromethane (100 mL), filtered with suction using diatomaceous earth, and the organic solvent was removed by distillation under reduced pressure. The intermediate R / S-22 (3.4 g, yield: 34%) was obtained by separation on a silica gel column.

[0183] Under air atmosphere, R / S-22 (10.1 g, 10.0 mmol) and m-chloroperbenzoic acid (2.2 g, 77 w%, 10.0 mmol) were added to a 150 mL three-necked flask, and 100 mL of dichloromethane was added to dissolve, and stirred at room temperature for 22 hours. Cooled to 0 ° C, m-chloroperbenzoic acid (0.7 g, 77 w%, 3.0 mmol) was added, and stirred at room temperature for 1 hour. Saturated sodium sulfite aqueous solution was added and stirred at room temperature, insoluble matter was filtered off, and the liquid was separated to take the organic layer. The solvent was removed by reduced pressure distillation, and compound R / S-II-113 (6.3 g, yield: 63%) was obtained by silica gel column separation. C63H47NO2P2Se; M / Z = 991.22, theoretical value 991.22 (100%), 992.23 (69.5%), 989.23 (63.0%), 990.23 (36.6%), 988.23 (28.4%), 993.23 (23.9%), 987.23 (18.9%), 993.22 (17.6%), 991.23 (1.8%), 986.23 (1.2%), 990.24 (1.1%); Elemental analysis: C, 76.36; H, 4.78; N, 1.41; O, 3.23; P, 6.25; S, 7.97.

[0184] Example 12

[0185] This example provides compound R / S-III-7, whose structural formula and synthesis route are as follows:

[0186]

[0187] The specific implementation steps are:

[0188] Under argon atmosphere, R / S-3 (9.6 g, 20.0 mmol), methyl 4-bromo-2-fluorobenzoate (5.1 g, 22.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 120 mL of N,N-dimethylformamide was added, and the temperature was raised to 110°C for reaction for 5 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-23 (11.0 g, yield: 80%).

[0189] Under air atmosphere, compound R / S-23 (6.9 g, 10.0 mmol) was added to a 250 mL three-necked flask, dissolved in 60 mL 1,4-dioxane, and KOH aqueous solution (10 mL, 10.0 M, 100.0 mmol) was added, and stirred at room temperature overnight. After the reaction was completed, hydrochloric acid (2.0 M) was added to the reaction solution to adjust the pH to neutral, filtered, and vacuum dried to obtain the intermediate R / S-24 (6.0 g, yield: 89%).

[0190] In an air atmosphere, compound R / S-24 (6.8 g, 10.0 mmol) was added to a 250 mL three-necked flask, followed by 60 mL of trifluoroacetic acid, and the mixture was cooled to 0°C. Trifluoroacetic anhydride (7.0 mL, 1.6 g / cm 3 , 50.0 mmol), refluxed at 50°C with stirring for 2 h. After the reaction was completed, saturated sodium bicarbonate aqueous solution was added to the reaction solution to adjust the pH to neutral, filtered, and vacuum dried. The obtained solid was separated by silica gel column to obtain compound R / S-25 (4.0 g, yield: 60%).

[0191] Under argon atmosphere, intermediate R / S-25 (6.6 g, 10.0 mmol), 10H-spiro[aza-9,9'-fluorene] (4.0 g, 12.0 mmol), tridibenzylideneacetone dipalladium (457.9 mg, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (290.1 ​​mg, 1.0 mmol), sodium tert-butoxide (1.9 g, 20.0 mmol) and toluene (60 mL) were added to a 100 mL bottle. The temperature was raised to 110°C and the reaction was carried out for 4 hours. After the reaction was completed, the mixture was extracted three times with dichloromethane and water to obtain the organic phase. The dichloromethane was removed by vacuum distillation, and the compound R / S-III-7 (6.6 g, yield: 72%) was obtained by silica gel column separation. C63H48NO5PS; M / Z = 909.34, theoretical value 909.34 (100%), 910.34 (69.9%), 911.34 (24.5%), 912.35 (5.4%), 913.35 (1.0%); elemental analysis: C, 84.47; H, 5.32; N, 1.54; O, 5.27; P, 3.40.

[0192] Example 13: This example prepares compound R / S-III-56, and its structural formula and synthesis route are shown below:

[0193]

[0194] The specific implementation steps are:

[0195] Under argon atmosphere, intermediate R / S-3 (4.8 g, 10.0 mmol), p-toluenesulfonic acid monohydrate (1.9 g, 10.0 mmol) and toluene (40 mL) were added to a 100 mL three-necked flask. After 10 minutes, N-iodosuccinimide (NIS) (2.2 g, 10.0 mmol) was added and stirred at room temperature for 8 hours. After the reaction was completed, saturated aqueous solution of Na2SO3 was added to quench, and 1.0 M aqueous hydrochloric acid was added to acidify. The aqueous layer was extracted twice with ethyl acetate, and the organic solvent was removed by vacuum distillation. The intermediate R / S-26 (4.3 g, yield: 71%) was obtained by silica gel column separation.

[0196] Under argon atmosphere, 2-fluoro-5-bromobenzene selenol (2.3 g, 11.0 mmol), R / S-26 (6.0 g, 10.0 mmol), cuprous iodide (95.2 mg, 0.5 mmol), ethylene glycol (0.6 g, 20.0 mmol) and potassium carbonate (2.8 g, 20.0 mmol) were added to a 250 mL three-necked flask, and 50 mL of isopropanol was added. The temperature was raised to 80°C and the reaction was carried out for 24 hours. After the reaction was completed, the solvent in the reaction system was dried by rotary evaporation, and the organic phase was extracted three times with dichloromethane and water. The dichloromethane was removed by vacuum distillation, and the intermediate R / S-27 (4.4 g, yield: 64%) was obtained by silica gel column separation.

[0197] Under argon atmosphere, R / S-27 (6.8 g, 10.0 mmol) and cesium carbonate (13.0 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 100 mL of N,N-dimethylformamide was added, and the temperature was raised to 180°C for 10 hours. After cooling to room temperature, saturated brine was added to the reaction solution, filtered, and vacuum dried. The solid obtained was separated by silica gel column to obtain intermediate R / S-28 (4.3 g, yield: 65%).

[0198] In an air atmosphere, R / S-28 (6.6 g, 10.0 mmol), m-chloroperbenzoic acid (mCPBA) (7.4 g, 75%, 30.0 mmol) and dichloromethane (120 mL) were added to a 250 mL three-necked flask and stirred at room temperature for 6 hours. After the reaction was completed, a saturated aqueous solution of Na2SO3 was added to quench the reaction, and the reaction was extracted three times with dichloromethane and water to obtain the organic phase. The dichloromethane was removed by vacuum distillation, and the intermediate R / S-29 (6.3 g, yield: 90%) was obtained by silica gel column separation.

[0199] Under argon atmosphere, intermediate R / S-29 (6.9 g, 10.0 mmol), spiro[acridine-9(10H), 9'-[9H]xanthene (4.2 g, 12.0 mmol), tridibenzylideneacetone dipalladium (457.9 mg, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (290.1 ​​mg, 1.0 mmol), sodium tert-butoxide (1.9 g, 20.0 mmol) and toluene (60 mL) were added into a 100 mL bottle. The temperature was raised to 110°C and the reaction was carried out for 4 hours. After the reaction was completed, the organic phase was extracted three times with dichloromethane and water. The dichloromethane was removed by vacuum distillation, and the compound R / S-III-56 (7.6 g, yield: 79%) was obtained after separation on a silica gel column. C63H48NO5PS; M / Z = 961.32, theoretical value 961.30 (100%), 962.30 (69.5%), 963.31 (23.4%), 964.31 (6.1%), 963.29 (4.5%), 964.30 (3.2%), 963.30 (1.1%), 965.30 (1.1%); Elemental analysis: C, 78.65; H, 5.03; N, 1.46; O, 8.31; P, 3.22; S, 3.33.

[0200] Embodiment 14

[0201] This example provides compound R / S-III-62, whose structural formula and synthesis route are as follows:

[0202]

[0203] The specific implementation steps are:

[0204] Under argon atmosphere, intermediate R / S-2 (6.1 g, 10.0 mmol), p-toluenesulfonic acid monohydrate (1.9 g, 10.0 mmol) and toluene (40 mL) were added to a 100 mL three-necked flask. After 10 minutes, N-iodosuccinimide (NIS) (2.2 g, 10.00 mmol) was added and stirred at room temperature for 8 hours. After the reaction was completed, saturated aqueous solution of Na2SO3 was added to quench, and 1.0 M aqueous hydrochloric acid solution was added to acidify. The aqueous layer was extracted twice with ethyl acetate, and the organic solvent was removed by vacuum distillation. The intermediate R / S-30 (4.8 g, yield: 65%) was obtained by silica gel column separation.

[0205] Under argon atmosphere, 4-bromo-1,2-benzenedithiol (2.4 g, 11.0 mmol), R / S-30 (7.4 g, 10.0 mmol), cuprous iodide (190.5 mg, 1.0 mmol), ethylene glycol (2.5 g, 40.0 mmol) and potassium carbonate (5.5 g, 40.0 mmol) were added to a 250 mL three-necked flask, and 50 mL of isopropanol was added. The temperature was raised to 80 ° C and reacted for 24 hours. After the reaction was completed, the solvent in the reaction system was dried, extracted with dichloromethane and water three times, and the organic phase was taken. Dichloromethane was removed by vacuum distillation, and the intermediate R / S-31 (2.7 g, yield: 40%) was obtained by silica gel column separation.

[0206] In an air atmosphere, R / S-31 (6.8 g, 10.0 mmol), m-chloroperbenzoic acid (mCPBA) (14.8 g, 75%, 60.0 mmol) and dichloromethane (120 mL) were added to a 250 mL three-necked flask and stirred at room temperature for 6 hours. After the reaction was completed, a saturated aqueous solution of Na2SO3 was added to quench the reaction, and the reaction was extracted three times with dichloromethane and water to obtain the organic phase. The dichloromethane was removed by vacuum distillation, and the intermediate R / S-32 (5.8 g, yield: 78%) was obtained by silica gel column separation.

[0207] Under argon atmosphere, in a 100mL side-mouth bottle, add intermediate R / S-32 (7.4g, 10.0mmol), (g, 12.0mmol), tridibenzylideneacetone dipalladium (457.9mg, 0.5mmol), tri-tert-butylphosphine tetrafluoroborate (290.1mg, 1.0mmol), sodium tert-butoxide (1.9g, 20.0mmol) and toluene (60mL). Heat to 110℃ and react for 4 hours. After the reaction is completed, extract with dichloromethane and water three times to take the organic phase. Remove dichloromethane by vacuum distillation, and separate on a silica gel column to obtain compound R / S-III-62 (6.6g, yield: 76%). C53H46NO5PS2; M / Z = 871.26, theoretical value 871.26 (100%), 872.26 (58.0%), 873.26 (18.4%), 874.27 (3.1%), 872.25 (2.0%), 874.26 (1.0%); Elemental analysis: C, 73.00; H, 5.32; N, 1.61; O, 9.17; P, 3.55; S, 7.35.

[0208] Comparative Example 1

[0209] This comparative example provides a comparative compound R / S-IV-1, whose structural formula and synthetic route are as follows:

[0210]

[0211] The specific implementation steps are:

[0212] The intermediate R / S-3 was replaced with an equivalent amount of 5,6,7,8-tetrahydro-2-naphthol (2.9 g, 20.0 mmol), and the other raw materials and steps were the same as in Example 1 to obtain compound R / S-IV-1 (1.2 g, yield 36%). C22H17BOS; M / Z = 340.10, theoretical value 340.11 (100%), 341.11 (25.7%), 339.11 (24.8%), 340.12 (6.0%), 342.11 (5.2%), 341.12 (1.0%); elemental analysis: C, 77.66; H, 5.04; B, 3.18; O, 4.70; S, 9.42.

[0213] Comparative Example 2

[0214] This comparative example provides a comparative compound R / S-IV-2, whose structural formula and synthetic route are as follows:

[0215]

[0216] The specific implementation steps are:

[0217] The intermediate R / S-2 was replaced with an equivalent amount of 5,6,7,8-tetrahydro-2-naphthyl-1,1,1-trimethylammonium sulfonate (5.6 g, 20.0 mmol), and the other raw materials and steps were the same as those in Example 8 to obtain compound R / S-II-52 (1.1 g, yield 18%). Molecular formula: C40H27BN2S; M / Z = 578.20, theoretical value 578.20 (100%), 579.20 (45.8%), 577.20 (24.7%), 580.21 (9.6%), 580.19 (4.7%), 581.21 (2.2%); elemental analysis: C, 83.04; H, 4.70; B, 1.87; N, 4.84; S, 5.54.

[0218] Comparative Example 3

[0219] This comparative example provides a comparative compound R / S-IV-3, whose structural formula and synthesis route are as follows:

[0220]

[0221] The specific implementation steps are:

[0222] In the first step, the raw material 5-phenyl-5,11-dihydroindole [3,2-B] carbazole was replaced with an equivalent amount of 3,6- (diphenylamino) carbazole (6.0 g, 12.0 mmol), and the other raw materials and steps were the same as those in Comparative Example 2 to obtain an intermediate; the other raw materials and steps were the same as those in Example 10 to obtain compound R / S-II-85 (1.3 g, yield 17%). Molecular formula: C52H38N3OPS; M / Z = 783.26, theoretical value 783.25 (100%), 784.25 (57.5%), 785.25 (16.8%), 578.24 (4.5%); elemental analysis: C, 79.67; H, 4.89; N, 5.36; O, 2.04; P, 3.95; S, 4.09.

[0223] Comparative Example 4

[0224] This comparative example provides a comparative compound R / S-IV-4, whose structural formula and synthetic route are as follows:

[0225]

[0226] The specific implementation steps are:

[0227] The intermediate R / S-3 was replaced with an equivalent amount of 5,6,7,8-tetrahydro-2-naphthol (3.0 g, 20.0 mmol), and the other raw materials and steps were the same as those in Example 12 to obtain compound R / S-IV-4 (2.3 g, yield 40%). Molecular formula: C42H29NO2; M / Z = 579.22, theoretical value 579.22 (100%), 580.22 (45.9%), 581.23 (10.3%), 582.23 (1.7%); elemental analysis: C, 87.02; H, 5.04; N, 2.42; O, 5.52.

[0228] Test example:

[0229] 1. The photophysical properties of the materials prepared in Examples 1-14 and Comparative Examples 1-4 were tested. Since the properties of the chiral enantiomers are basically the same, the S enantiomer is taken as an example to show the relevant data except the luminescence asymmetry factor. The test results are shown in Table 1:

[0230] Table 1 Photophysical properties of the compounds obtained in Examples 1 to 14 and Comparative Examples 1 to 4

[0231]

[0232]

[0233] Table 1 Data Notes: ΔE ST is the difference between the singlet energy level and the triplet energy level.5 The sample was dissolved in toluene solution at a concentration of 1 mol / L to prepare the tested sample, and the difference between the onset value of the fluorescence spectrum and the phosphorescence spectrum was measured. The delayed fluorescence lifetime and luminescence asymmetry factor were obtained by preparing the compound into a film sample and testing it using a time-resolved fluorescence spectrometer.

[0234] The above-mentioned self-host chiral organic light-emitting small molecule material with thermally activated delayed fluorescence characteristics of the present invention can be applied to the light-emitting layer in OLED devices. Since the properties of chiral enantiomers are basically the same, the relevant data of the device are shown by taking the S enantiomer as an example.

[0235] 2. Ultraviolet absorption spectrum, fluorescence spectrum

[0236] The UV absorption spectrum and fluorescence spectrum of the compound obtained in the test example in the solution, wherein the solution is a toluene solution, tetrahydrofuran, or a water / tetrahydrofuran mixed solvent (wherein the percentage of water is 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%), and the concentration of the compound in the solution is 1×10 -5 mol L -1 , Figure 1 The ultraviolet absorption spectrum and fluorescence spectrum of the compound S-II-52 obtained in Example 8 in toluene solution; Figure 2 The ultraviolet absorption spectrum and fluorescence spectrum of the compound S-III-56 obtained in Example 13 in a toluene solution at room temperature; Figure 3 This is the fluorescence spectrum of compound S-III-56 obtained in Example 13 in mixed solvents of water / tetrahydrofuran at different ratios. Figure 4 This is the transient fluorescence lifetime spectrum of compound S-III-7 obtained in Example 12. Figure 5 This is the photoinduced circularly polarized luminescence spectrum of compound S-III-7 obtained in Example 12.

[0237] Device Example:

[0238] Device Examples 1-4 and Comparative Device Examples 1-2 provide non-doped OLED devices, wherein compounds SI-1, SI-53, S-II-62, S-III-7, S-IV-2 and S-IV-4 are used as light-emitting layer materials of the non-doped OLED devices; the structure of the non-doped OLED device is as follows:

[0239] ITO (95nm) / TAPC (20nm) / EML (35nm) / TmPyPB (55nm) / LiF (1nm) / Al (100nm) ITO is the anode, TAPC is the hole injection layer, TmPyPB is the electron transport layer, LiF is the electron injection layer, and Al is the cathode. The EML materials are shown in Table 2.

[0240] The structural formulas of some of the materials used are as follows:

[0241]

[0242] The current-brightness-voltage characteristics of the device were measured by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode. All tests were completed in room temperature atmosphere. The test results are shown in Table 2.

[0243] Table 2 Device performance

[0244]

[0245]

[0246] Among them, the embodiments in Table 2 are device embodiments; the comparative examples are device comparative examples;

[0247] It can be seen from Table 2 that the device embodiment of the present invention embodies the following technical effects:

[0248] Compared with the luminescent small molecules S-IV-2 and S-IV-4 without diphenylphosphine oxide modification, the autonomous small molecules S-II-62 and S-III-7 with diphenylphosphine oxide showed significantly higher maximum external quantum efficiency and current efficiency, as well as lower turn-on voltage under the same non-doped device structure. The device performance was significantly improved, and the non-doped device was endowed with circularly polarized luminescence characteristics, indicating that this type of autonomous small molecule can suppress the quenching effect caused by the close stacking of molecules in non-doped devices to a certain extent, fully reflecting its autonomous characteristics and advantages.

[0249] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A self-host chiral organic light-emitting compound, characterized in that: Has the following structure: wherein X is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)- or -(C=O)-; Y is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)-, -(C=O)-, Ar1 is selected from a substituted or unsubstituted C5-C80 aryl ring, or a substituted or unsubstituted C3-C80 aryl heterocycle; When Y is selected from -O-, -S-, -Se-, -Te-, -C(H2)-, -S(O2)- or -(C=O)-, Ar2 is absent; When Y is selected from When Ar2 is present, it is selected from a substituted or unsubstituted C5-C80 aryl ring, or a substituted or unsubstituted C3-C80 aryl heterocycle; The substituents in the substituted C5-C80 aryl ring and the substituted C3-C80 aryl heterocycle are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl; the heteroatoms in the heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se; R, R ’ Respectively represent Ar and Ar ’ Substituents on ’ Each is independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl; n、n ’ Ar, Ar ’ The number of substituents on Ar, Ar ’ Can exist independently or linked.

2. The self-host chiral organic light-emitting compound according to claim 1, characterized in that: The self-host chiral organic light-emitting compound has a structure shown in the following formula-1-1 or formula-1-2: Wherein, X and X1 are independently selected from -O-, -S-, -Se-, -Te-; Y is selected from Ar1 and Ar2 are each independently selected from a substituted or unsubstituted C5-C60 aryl ring, or a substituted or unsubstituted C3-C60 aryl heterocycle; The substituents in the substituted C5-C60 aryl ring and the substituted C3-C60 aryl heterocyclic ring are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl; the heteroatoms in the substituted C3-C60 aryl heterocyclic ring and C3-C60 heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se; R1, R2, and R3 represent substituents on Ar1, Ar2, and Ar3, respectively; R1, R2, and R3 are independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl; n1, n2, n3 represent the number of substituents on Ar1, Ar2, Ar3, and n1, n2, n3 are each independently selected from integers of 0 to 5; In Formula 1-2, Ar1, Ar2, and Ar3 exist independently or in combination.

3. The self-host chiral organic light-emitting compound according to claim 1 or 2, characterized in that: In Formula 1-2, Ar1 and Ar3 are connected by a single bond, -C(L1L2)-, -(C=O)-, -N(L1)-, -O-, -S-, -Se-, -Te-, -S(O2)- or Link; The L1-L2 are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se; The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl; Preferably, in Formula 1-2, Ar2 and Ar3 are connected by single bonds, -C(L1L2)-, -(C=O)-, -N(L1)-, -O-, -S-, -Se-, -Te-, -S(O2)-, Link; The L1-L2 are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se; The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

4. The self-host chiral organic light-emitting compound according to any one of claims 1 to 3, characterized in that: The Ar1, Ar2, and Ar3 are each independently selected from one of the following rings: Wherein, each of L1 to L2 is independently selected from substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 alkylthio, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3 to C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se; The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

5. The self-host chiral organic light-emitting compound according to any one of claims 1 to 4, characterized in that: The self-host chiral organic light-emitting compound has a structure shown in the following formula-1-3 or formula-1-4: X3, X4 are independently selected from -C(H2)-, -S(O2)-, -O- or -(C=O)-; Ar4 is an electron donating group selected from substituted or unsubstituted C3-C60 heteroaryl groups; the substituents in the substituted C3-C60 heteroaryl groups are selected from H, D, F, Cl, Br, I, alkenyl, alkynyl, nitrile, acyl, alkoxy, sulfone, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C60 aryl, C3-C60 heteroaryl groups; the heteroatoms in the C3-C60 heteroaryl groups and the substituted or unsubstituted C3-C60 aromatic heterocycles are selected from one or more of Si, Ge, N, P, O, S and Se.

6. The self-host chiral organic light-emitting compound according to any one of claims 1 to 5, characterized in that: The Ar4 is independently selected from one of the following groups: Wherein, each of L1 to L2 is independently selected from H, D, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 alkylthio, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3 to C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se; The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

7. The self-host chiral organic light-emitting compound according to any one of claims 1 to 6, characterized in that: The structure of the self-host chiral organic light-emitting compound is selected from any one of the following structures: Wherein, R1-R4 are each independently selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, C3-C30 heteroaryl; n1 to n4 are the numbers of R1 to R4, respectively, and n1 to n4 are each independently selected from integers of 0 to 5; The L1-L2 are each independently selected from H, D, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the heteroatom in the substituted or unsubstituted C3-C30 heteroaryl is selected from one or more of Si, Ge, N, P, O, S and Se; The substituents in the substituted C1-C10 alkyl, substituted C3-C30 cycloalkyl, substituted C1-C30 alkylthio, substituted C6-C30 aryl, and substituted C3-C30 heteroaryl are selected from H, D, F, Cl, Br, I, nitrile, acyl, alkoxy, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkylthio, C6-C30 aryl, and C3-C30 heteroaryl.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic layer located between the anode and the cathode, wherein the organic layer comprises the self-host chiral organic light-emitting compound according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises the self-host chiral organic light-emitting compound according to any one of claims 1 to 7.

10. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to claim 8 or 9.

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