Self-sensitized organic light-emitting material with spiro structure and organic electroluminescent device thereof

Abstract

The present application relates to the technical field of organic photoelectric material, in particular to a kind of self-sensitization thermally activated delayed fluorescence organic light emitting display material with spiro structure and organic electroluminescent device thereof.The material is compound with the structure shown in formula (G), which is used as connecting group by rigid spiro skeleton to fix luminescent unit, donor group and acceptor group in space as face-to-face and close arrangement, so that suitable energy transfer radius and energy transfer dipole-dipole orientation are formed between luminescent unit and sensitization unit, thereby realizing efficient energy transfer, finally realizing narrow-band luminescence almost consistent with luminescent unit and high-efficiency stable electroluminescent device.Secondly, such material can simplify the composition of light-emitting layer in organic electroluminescent device, not only reduce the cost of material, but also simplify the preparation process of organic electroluminescent device, thereby facilitating commercial application.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, specifically to a class of self-sensitized organic light-emitting materials with a helical ring structure and their organic electroluminescent devices. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are widely considered the third generation of display technology after cathode ray tubes and liquid crystal displays (LCDs) due to their advantages such as self-illumination, flexibility, high color gamut, wide viewing angle, and fast response. After more than 30 years of accumulation and development, OLED technology has gradually matured and is gradually replacing LCDs in the display field; in the field of solid-state lighting, OLEDs are also expected to replace incandescent lamps and fluorescent lamps, becoming a new generation of high-quality light sources.

[0003] OLEDs are carrier-dual-injection light-emitting devices, composed of positive and negative electrodes and multiple layers of organic thin-film functional layers. The organic functional layer material is a key factor determining device performance, and the core functional material is the light-emitting material, directly determining the OLED's luminescent properties. Historically, OLED light-emitting materials have been divided into three generations: the first generation uses fluorescent materials, the second generation uses phosphorescent materials, and the third generation uses thermally activated delayed fluorescence (TADF). Due to spin-forbidden limitations, OLEDs based on first-generation fluorescent materials can only emit light using singlet excitons, resulting in an internal quantum efficiency of less than 25%. OLEDs based on second-generation phosphorescent materials introduce noble metal atoms into the molecular structure, enabling triplet excitons to emit phosphorescence through spin-orbit coupling, achieving a 100% internal quantum efficiency. However, the noble metal resources required for phosphorescent materials are scarce and expensive. Furthermore, the low dissociation energy of the metal coordination bonds in phosphorescent molecules means that the stability of deep blue phosphorescent devices has consistently fallen short of practical application requirements. In recent years, Professor Adachi's research group at Kyushu University in Japan has used molecular design to narrow the energy gap (ΔE) between the lowest excited singlet and lowest excited triplet states of charge-transfer molecules. ST By controlling the fluorescence intensity within a sufficiently small range (<0.3 eV), the molecule exhibits thermally activated delayed fluorescence (TADF) properties, meaning that triplet excitons can undergo reverse intersystem crossing transitions to singlet states and emit fluorescence. Therefore, luminescent materials with TADF properties combine the advantages of fluorescent and phosphorescent materials, achieving 100% internal quantum efficiency in OLEDs while reducing device material costs, thus earning them the reputation of third-generation OLED luminescent materials.

[0004] The most commonly used TADF molecular design strategy currently involves introducing donor and acceptor groups into the molecule to reduce the overlap integral of the molecular frontier orbitals, thereby reducing the ΔE of the molecule. ST However, according to Fermi's golden rule, a decrease in the overlap integral of molecular orbitals at the molecular frontier leads to a reduction in the radiative transition rate of the material. This means that there is a mutual constraint between the rapid reverse intersystem crossing rate and the radiative transition rate of TADF materials. This constraint slows down the exciton dynamics, resulting in a significant efficiency roll-off and poor stability of the device at high brightness. Furthermore, since TADF materials emit light in a charge-transfer state, their emission spectrum is broad and their color purity is low, making it difficult to meet current requirements for ultra-high-definition displays, thus further limiting their development and application. To address these issues, a thermally activated sensitized fluorescence (TRF) mechanism has emerged. This mechanism uses TADF materials as a sensitizer in traditional fluorescent materials. Its main function is to convert its triplet excitons into singlet excitons through a reverse intersystem crossing process, and then... Energy is transferred to fluorescent luminescent materials with high color purity, sensitizing the fluorescent molecules to emit light. By combining the efficient utilization of excitons by TADF materials with the fast radiative transition rate and narrow spectral characteristics of fluorescent materials, this mechanism successfully overcomes the limitations of using TADF materials as luminescent materials.

[0005] However, existing thermally activated sensitized fluorescence (TRF) technologies still face numerous challenges. First, the use of a ternary system (host material, sensitizer material, and luminescent material) as the luminescent layer not only increases material costs but also enhances the complexity of device fabrication, making it difficult to integrate with existing manufacturing processes and thus limiting its commercial viability. Second, current TRF technologies generally employ doping processes, resulting in a large distance between sensitizer and luminescent molecules, and their random arrangement leads to low energy transfer efficiency. This causes some sensitizer molecules to also participate in luminescence, making it difficult for the obtained electroluminescence spectrum to match the emission spectrum of the luminescent molecules, thus limiting the improvement of device color purity. More importantly, excitons not transferred to the luminescent molecules are extremely detrimental to device stability. Furthermore, designing matching deep blue photosensitizer molecules for deep blue luminescent molecules presents significant challenges. Summary of the Invention

[0006] The problem the invention aims to solve

[0007] The purpose of this invention is to provide a class of self-sensitized organic light-emitting materials with a spirocyclic structure and their organic electroluminescent devices. The molecular structure of this material contains both sensitizing units with thermally activated delayed fluorescence (TEF) properties and light-emitting units with narrow-band emission, thereby constructing a thermally activated delayed fluorescence material with self-sensitized properties. The spirocyclic structure possesses unique non-planar helical conjugation effects, orthogonal conformations, and steric hindrance effects, which can effectively improve the photoelectric performance and stability of organic semiconductor materials. The spirocyclic structure can act as a rigid bridging group, connecting donor and acceptor groups, enabling the simultaneous achievement of a small ΔE. ST This invention achieves high luminescence efficiency and constructs high-performance thermally activated delayed fluorescence materials. It utilizes a rigid spirocyclic framework as a connecting group to spatially confine the luminescent unit, donor group, and acceptor group into a face-to-face and closely spaced arrangement, ensuring suitable spacing between the luminescent unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of the energy transfer enable efficient energy transfer, ultimately achieving narrow-band emission almost identical to the light-emitting unit and a highly efficient and stable electroluminescent device. Secondly, this type of material simplifies the composition of the light-emitting layer in organic electroluminescent devices, reducing material costs and simplifying the fabrication process, thus facilitating commercial applications.

[0008] Solution for solving the problem

[0009] This invention provides a self-sensitizing material system that can ensure a suitable relationship between the luminescent unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of energy transfer not only achieve narrow-band emission almost identical to the light-emitting unit and efficient and stable electroluminescence, but also simplify the fabrication process of organic electroluminescent devices. The specific scheme is as follows:

[0010] In a first aspect, the present invention provides a compound having the structure shown in formula (G), which can be used as a self-sensitized thermally activated delayed fluorescence organic light-emitting display material:

[0011]

[0012] in,

[0013] X represents -C(R) a (R) b )-、-NR a -、-BiR a -、-BR a -、-Si(R a (R) b )-、-Ge(R a (R) b)-, -O-, -S-, -Se-, -Te-, -S(=O)2-,

[0014] -C(=O)-、-P(=O)(R a - or single bond;

[0015] F1 and F2 each independently represent -C(R) a (R) b )-、-NR a -、-BiR a -、-BR a -、-Si(R a (R) b )-、-Ge(R a (R) b )-, -O-, -S-, -Se-, -Te-, -S(=O)2-, -C(=O)-, -P(=O)(R a - or a single bond or none at all; when at least one of F1 and F2 is absent, the carbon atom attached to it is capped with hydrogen;

[0016] Each R a R b Each independently represents hydrogen, deuterium, halogen atoms, and C1-C atoms. 15 Alkyl or C6-C 18 Aryl;

[0017] R1-R 15 Each independently represents hydrogen, deuterium, halogen atom, cyano, nitro, hydroxyl, amino, mercapto, optionally with one or more R groups. c Replacement C1-C 15 Alkyl, optionally with one or more R c Replacement C1-C 15 Halogenated alkyl, optionally with one or more R c Replacement C1-C 15 Alkoxy, optionally with one or more R c Replacement -S(C1-C) 15 Alkyl), optionally with one or more R c Substituted -Si(R) 16 (R) 17 (R) 18 ), can be arbitrarily controlled by one or more R c Replacement -N(R) 16 (R) 17 ), can be arbitrarily controlled by one or more R c Replacement C6-C 18 aryl or optionally substituted with one or more R c Substituted 5-18 heteroaryl groups;

[0018] Each R 16 R 17 R 18 Each independently represents hydrogen, C1-C 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl groups;

[0019] Each R c Each represents C1-C independently. 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl groups;

[0020] E represents arbitrarily selected by one or more R. d Replacement C6-C 120 aryl, optionally with one or more R e The substituted 5-120 heteroaryl group or optionally replaced by one or more R f Replacement Wherein, * indicates a linking bond of a group; D1 represents B or N; D3 represents -C(=O)- or -S(=O)2- or is absent, and when D3 is absent, the carbon atom attached to it is hydrogen-terminated; D2 represents -N(Ar)-, -P(=O)(Ar)-, -C(=O)- or -S(=O)2-; D4 represents -O-, -S-, -Se-, -Te-, -N(Ar)-, -P(=O)(Ar)-, -C(=O)- or -S(=O)2-; each Ar independently represents an atom optionally bounded by one or more R groups. g Replacement C6-C 18 aryl or optionally substituted with one or more R g The substituted 5-18 heteroaryl groups, each Ar, may optionally exist independently or via a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R) h - is attached to an unsubstituted carbon atom on an adjacent aryl or heteroaryl group;

[0021] Each R d Each independently represents a cyano group, optionally with one or more R groups. h Replacement C1-C 15 Alkyl, optionally with one or more R h Replacement C6-C 18 aryl or optionally substituted with one or more R h Replacement -N(R) x )2; Each R x Each represents C1-C independently. 15 Alkyl or C6-C 18 Aryl;

[0022] Each Re R f R g Each independently represents a cyano group, optionally with one or more R groups. h Replacement C1-C 15 Alkyl, optionally with one or more R h Replacement C6-C 18 aryl, optionally with one or more R h The substituted 5-18 heteroaryl group or optionally replaced by one or more R h Replacement -N(R) y )2; Each R y Each represents C1-C independently. 15 Alkyl or C6-C 18 Aryl;

[0023] Each R h Each represents C1-C independently. 15 Alkyl groups or optionally one or more C6-C 18 Aryl-substituted C6-C 18 Aryl;

[0024] A represents any one or more R's. i Replacement Optional by one or more R i Replacement Or C6-C substituted with one or more cyano groups 18 Aryl; where * indicates a linking bond; D5, D6, and D7 each independently represent N or CH, and at least one is N; D8, D9, and D 10 Each represents C1-C independently. 15 Alkyl, C1-C 15 cycloalkyl, C6-C 18 Aryl or 5-18 heteroaryl groups, or none at all; D 11 D 12 Each can independently represent -O-, -S-, -S(=O)2, -Se-, or -Te-, or may not exist;

[0025] Each R i Each represents C1-C independently. 15 Alkyl, C1-C 15 Haloalkyl, C6-C 18 Aryl or 5-18 heteroaryl groups;

[0026] K1 and K2 independently represent C1-C 15 Alkyl, optionally with one or more R j Replacement C6-C 18 aryl or optionally substituted with one or more R jThe substituted 5-18 heteroaryl groups may not exist;

[0027] Each R j Each represents C1-C independently. 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl compounds.

[0028] In some implementations, E represents optional being controlled by one or more Rs. f The following groups are substituted:

[0029]

[0030] Where Y1 represents a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R) h - or does not exist, R h Having the definition described in formula (G); D4 having the definition described in formula (G); n is selected from any integer from 0 to 3; * represents the linking bond of the group; R f It has the definition described in equation (G).

[0031] In some preferred embodiments, E represents optional being controlled by one or more R f The following groups are substituted:

[0032]

[0033] Where Y1 and Y2 independently represent single bonds, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R)-. h - or does not exist, R h It has the definition described in formula (G); Y3 represents a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, or -S(=O)2-; * represents a linking bond of a group; R f It has the definition described in equation (G).

[0034] In some preferred embodiments, E represents optionally being controlled by one or more Rs. f The following groups are substituted:

[0035]

[0036] Where * represents the linking bond of a group; R f It has the definition described in equation (G).

[0037] In some implementations, E represents optional being controlled by one or more Rs. f The following groups are substituted:

[0038]

[0039] Where Z1 and Z2 independently represent -N(Ar)-, -P(=O)(Ar)-, -C(=O)-, or -S(=O)2-; Z3 represents -N(Ar)-, -P(=O)(Ar)-, -C(=O)-, or -S(=O)2-, or is absent; * indicates the linking bond of the group; Ar, R f It has the definition described in equation (G).

[0040] In some preferred embodiments, E represents optional being controlled by one or more R f The following groups are substituted:

[0041]

[0042] Where * represents the linking bond of a group; R f It has the definition described in equation (G).

[0043] In some implementations, E represents optional being controlled by one or more Rs. d The following groups are substituted:

[0044]

[0045] Where n is selected from any integer from 1 to 4, preferably 1 or 2; * represents the linking bond of the group; R d It has the definition described in equation (G).

[0046] In some preferred embodiments, E represents optional being controlled by one or more R d The following groups are substituted:

[0047]

[0048] Where * represents the linking bond of a group; R d It has the definition described in equation (G).

[0049] In some implementations, E represents optional being controlled by one or more Rs. e The following groups are substituted:

[0050]

[0051] Where Ar1 and Ar2 each independently represent arbitrarily selected by one or more R e Replacement C6-C 18 aryl or optionally substituted with one or more R e The substituted 5-18 membered heteroaryl groups, Ar1 and Ar2, are each independently and optionally linked to an unsubstituted carbon atom on an adjacent aryl or heteroaryl group via a single bond; Re It has the definition described in formula (G); * indicates the linking bond of the group.

[0052] In some preferred embodiments, E represents optional being controlled by one or more R e The following groups are substituted:

[0053]

[0054] Among them, R e It has the definition described in formula (G); * indicates the linking bond of the group.

[0055] In some implementations, A represents optional being controlled by one or more Rs. i The following groups are substituted:

[0056]

[0057] Where * represents the linking bond of a group; R i It has the definition described in equation (G).

[0058] In some implementations, X represents -C(R) a (R) b -, -O-, -S-, -Se-, -Te- or single bond; R a R b Each independently represents hydrogen or C1-C. 15 alkyl.

[0059] In some preferred embodiments, X represents -O- or a single bond.

[0060] In some implementations, K1 and K2 independently represent C1-C 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl groups may not exist.

[0061] In some preferred embodiments, K1 and K2 each independently represent phenyl or are absent.

[0062] In some implementations, F1 and F2 independently represent -C(R) a (R) b -, -O-, -S-, -Se-, -Te- or single bonds or none at all; when at least one of F1 and F2 is absent, the carbon atom attached to it is hydrogen-terminated; R a R b Each independently represents hydrogen or C1-C. 15 Alkyl; preferably, R a R b Each represents C1-C independently. 15Alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl (e.g., methyl, ethyl, propyl, tert-butyl, etc.).

[0063] In some implementations, R1 represents hydrogen, halogen atom, C1-C 15 Alkyl, C1-C 15 Haloalkyl, C1-C 15 Alkyl groups, -S(C1-C 15 alkyl), -Si(R) 16 (R) 17 (R) 18 ), can be arbitrarily controlled by one or more R c Replacement -N(R) 16 (R) 17 C6-C 18 Aryl or 5-18 heteroaryl; each R 16 R 17 R 18 Each independently represents hydrogen, C1-C 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl; each R c Each represents C1-C independently. 15 alkyl.

[0064] In some preferred embodiments, R1 represents hydrogen, C1-C 15 Alkyl or optionally with one or more R c Replacement -N(R) 16 (R) 17 ); R 16 R 17 Each represents C6-C independently. 18 Aryl; each R c Each represents C1-C independently. 15 alkyl.

[0065] In some preferred embodiments, R1 represents hydrogen or C1-C. 15 Alkyl groups, preferably hydrogen or C1-C 10 Alkyl, more preferably hydrogen or C1-C5 alkyl (e.g., methyl, ethyl, propyl, tert-butyl, etc.).

[0066] In some implementation schemes, R5, R8, R 11 Each independently represents hydrogen, C1-C 15 Alkyl or C6-C 18 Aryl.

[0067] In some preferred embodiments, R5, R8, R 11 Each independently represents hydrogen or C1-C.15 Alkyl groups, preferably hydrogen or C1-C 10 Alkyl, more preferably hydrogen or C1-C5 alkyl (e.g., methyl, ethyl, propyl, tert-butyl, etc.).

[0068] In some implementation schemes, R2-R4, R6-R7, R9-R 10 R 12 -R 15 It represents hydrogen.

[0069] In some embodiments, the compounds of the present invention having the structure shown in formula (G) have the structure shown in formula (G-1):

[0070]

[0071] Among them, X, F1, F2, R1, R5, R8, R 11 E, A, K1, K2 have the definitions as described in formula (G) or the definitions above.

[0072] In some embodiments, the compounds of the present invention having the structure shown in formula (G) have the structure shown in formula (G-2):

[0073]

[0074] Among them, X, F1, F2, R1, R5, R8, R 11 A, K1, and K2 have the definitions described in equation (G) or the definitions above; R 20 R 21 R 22 R 23 Each independently represents hydrogen, C1-C 15 Alkyl or C6-C 18 Aryl group, preferably hydrogen or C1-C 15 Alkyl, more preferably hydrogen or C1-C 10 Alkyl, more preferably hydrogen or C1-C5 alkyl.

[0075] In some embodiments, the compounds of the present invention having the structure shown in formula (G) have the structure shown in formula (G-3):

[0076]

[0077] Among them, X, F1, F2, R1, R5, R8, R 11 A, K1, and K2 have the definitions described in equation (G) or the definitions above; R 24 R 25 R 26 Each independently represents hydrogen, C1-C 15 Alkyl or C6-C18 Aryl group, preferably hydrogen or C1-C 15 Alkyl, more preferably hydrogen or C1-C 10 Alkyl, more preferably hydrogen or C1-C5 alkyl.

[0078] Secondly, the present invention provides the following compounds, which can be used as self-sensitized thermally activated delayed fluorescence organic light-emitting display materials:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Thirdly, the present invention provides a method for preparing the above-mentioned compounds. The compounds having the structure shown in general formula (G) of the present invention can be prepared by the following reaction scheme:

[0103] Step 1 (Reaction 1):

[0104]

[0105] Step 2 (Reaction 2):

[0106]

[0107] Step 3 (Reaction 3):

[0108]

[0109] in,

[0110] X, R1-R 15 Compounds F1, F2, K1, K2, E, and A that have the definition described in the first aspect, or compounds having the structure of formula (G), are compounds described in the second aspect;

[0111] X1, X2, and X3 each independently represent halogen atoms, such as fluorine, chlorine, bromine, and iodine;

[0112] bpin means R 30 -R 33 Each represents C1-C independently. 15 Alkyl groups, * indicates the linking bond of the group.

[0113] In some embodiments, the reaction in step 1 is carried out in the presence of the catalyst tetra(triphenylphosphine)palladium and potassium carbonate.

[0114] In some embodiments, the reaction in step 2 is carried out in the presence of the catalyst tetra(triphenylphosphine)palladium and potassium carbonate.

[0115] In some implementations, the reaction in step 3 is carried out in the presence of n-butyllithium, glacial acetic acid, and concentrated hydrochloric acid.

[0116] Fourthly, the present invention provides an organic electroluminescent device, which, from bottom to top, comprises a substrate, a first electrode, an organic functional material layer, and a second electrode, wherein the organic functional material layer comprises:

[0117] The hole transport region is located above the first electrode;

[0118] A light-emitting layer, located above the hole transport region, comprises a host material and a light-emitting material;

[0119] The electron transport region is located above the light-emitting layer;

[0120] The light-emitting layer comprises a compound according to the first or second aspect.

[0121] In some embodiments, the luminescent material in the luminescent layer includes compounds according to the first or second aspect.

[0122] In some embodiments, the organic functional material layer further includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0123] Fifthly, the present invention provides a display device comprising the organic electroluminescent device according to the fourth aspect.

[0124] In a sixth aspect, the present invention provides a lighting device comprising an organic electroluminescent device according to the fourth aspect.

[0125] The effects of the invention

[0126] The organic light-emitting material of the present invention uses a rigid spirocyclic framework as a linking group to spatially confine the light-emitting unit, donor group, and acceptor group into a face-to-face and close arrangement, thereby achieving a suitable relationship between the light-emitting unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of the energy transfer are used to achieve efficient energy transfer, ultimately realizing narrow-band emission almost identical to the light-emitting unit and a highly efficient and stable electroluminescent device. The confined donor-acceptor groups form a charge-transfer state in space (i.e., a space charge-transfer state), and the energy difference (ΔE) between its lowest excited singlet state (S1) and lowest excited triplet state (T1) is... ST The voltage will reach a sufficiently small range (<0.1 eV), allowing triplet excitons to cross over to singlet states via reverse intersystem crossing, thus exhibiting excellent thermally activated delayed fluorescence characteristics and becoming sensitizing units. Simultaneously, under the constraint of a rigid spirocyclic framework, there is a suitable [emission / reduction] between the luminescent unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of energy transfer enable the energy of the sensitization units in this type of material to be transferred via intramolecular fluorescence resonance energy transfer. This allows for efficient energy transfer (FRET) to the light-emitting unit, ultimately achieving narrow-band emission almost identical to that of the light-emitting unit and a highly efficient and stable electroluminescent device. Secondly, this type of material simplifies the composition of the light-emitting layer in organic electroluminescent devices, reducing material costs and simplifying the fabrication process, thus facilitating commercial applications. Attached Figure Description

[0127] Figure 1 This is a schematic diagram illustrating the principle of the thermally activated delayed fluorescence property of the material of the present invention.

[0128] Figure 2 This is a simplified structural diagram of the organic electroluminescent device of the present invention; wherein, 1 is a glass substrate, 2 is a transparent anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode.

[0129] Figure 3 The UV absorption spectra of materials BNO, DM-C, and BNO-4 measured in toluene are shown.

[0130] Figure 4 This is the ultraviolet absorption spectrum of material BNN-1 measured in toluene.

[0131] Figure 5 The fluorescence spectra of materials Perylene-1, NPO-4, BNN-26, and BNONO-1 measured in toluene are shown.

[0132] Figure 6 The fluorescence spectra of materials BNOCz-1, NAJCz-5, BPX-7, and BNO-23 measured in toluene are shown.

[0133] Figure 7 The fluorescence spectra of material BNO-4 in different solvents are shown.

[0134] Figure 8 The fluorescence spectra of material BNN-1 in different solvents are shown.

[0135] Figure 9 The fluorescence spectra of materials BNO, DM-C, and BNO-4 measured in toluene are shown.

[0136] Figure 10 The fluorescence spectra of materials BNO, DM-C, and BNO-4 measured in N,N-dimethylformamide are shown.

[0137] Figure 11 The transient photoluminescence decay spectra of materials BNO-4 and BNO in toluene are shown.

[0138] Figure 12 The transient photoluminescence decay spectra of materials BNN-1 and BNN in toluene are shown.

[0139] Figure 13 For material BNN-1 1 H NMR spectrum.

[0140] Figure 14 For material BNO-4 1 H NMR spectrum. Detailed Implementation

[0141] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0142] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0143] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0144] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0145] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0146] The organic light-emitting material of the present invention is a compound having the structure shown in formula (G), such as Figure 1 As shown, this type of material uses a rigid spirocyclic framework as a connecting group to spatially confine the luminescent unit (E in general formula (G)), the donor group, and the acceptor group (A in general formula (G)) to a face-to-face and close arrangement, thereby achieving a suitable connection between the luminescent unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of the energy transfer are used to achieve efficient energy transfer, ultimately realizing narrow-band emission almost identical to the light-emitting unit and a highly efficient and stable electroluminescent device. The confined donor-acceptor groups form a charge-transfer state in space (i.e., a space charge-transfer state), and the energy difference (ΔE) between its lowest excited singlet state (S1) and lowest excited triplet state (T1) is... ST When the voltage reaches a sufficiently small range (<0.1 eV), the triplet exciton can cross over to the singlet state via reverse RISC, thus exhibiting excellent thermally activated delayed fluorescence characteristics and becoming a TADF sensitizing unit. Simultaneously, under the constraint of a rigid spirocyclic framework, there is a suitable [emission / reduction] relationship between the luminescent unit and the sensitizing unit. The energy transfer radius and dipole-dipole orientation of energy transfer enable the energy of the sensitization units in this type of material to be transferred via intramolecular fluorescence resonance energy transfer. Energy transfer (FRET) is achieved by radiating light (F) onto the light-emitting unit, thereby realizing efficient energy transfer and ultimately achieving narrow-band emission that is almost identical to that of the light-emitting unit, as well as a highly efficient and stable electroluminescent device.

[0147] In this invention, the lowest excited singlet state energy of the donor group and acceptor group (A) as sensitization units is greater than the lowest excited singlet state energy of the luminescent unit (E).

[0148] In this invention, the fluorescence emission spectra of the donor group and acceptor group (A) as sensitization units overlap with the ultraviolet absorption spectra of the luminescent unit (E).

[0149] [Terminology Definition]

[0150] In this invention, the range of values ​​represented by "value A to value B" refers to the range that includes the endpoint values ​​A and B.

[0151] In this invention, when "room temperature" or "room temperature" is used, the temperature can be 15°C to 30°C, or more specifically 15°C to 25°C, for example, 20°C.

[0152] <halogen atom>

[0153] In this invention, "halogen atom" refers to fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine.

[0154] <alkyl>

[0155] In this invention, "alkyl" refers to a monovalent saturated aliphatic hydrocarbon group, which can be a straight-chain group or a branched group. The alkyl group in this invention can be "C1-C2". 15 "Alkyl" refers to a group that is alkyl, and the number of carbon atoms in the carbon chain is between 1 and 15, preferably "C1-C".10 "alkyl", "C1-C5 alkyl" or "C1-C3 alkyl". The alkyl group in this invention can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, etc.

[0156] <halogenated alkyl>

[0157] In this invention, "halogenated alkyl" refers to an alkyl group as defined above in which one, two, or more hydrogen atoms are replaced by halogen atoms. The haloalkyl group in this invention can be "C1-C2". 15 "Halogenated alkyl", preferably "C1-C" 10 "Halogenated alkyl", "C1-C5 haloalkyl" or "C1-C3 haloalkyl". Representative examples of haloalkyl include -CCl3, -CF3, -CHCl2, CH2Cl, CH2Br, CH2I, -CH2CF3, -CF2CF3, etc.

[0158] <alkoxy>

[0159] In this invention, "alkoxy" refers to an -O-alkyl group, as defined above. The alkoxy group in this invention can be "C1-C2". 15 "alkoxy group", preferably "C1-C" 10 Alkoxy, C1-C5 alkoxy, or C1-C3 alkoxy. Representative examples include methoxy, ethoxy, propoxy, tert-butoxy, pentooxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, etc.

[0160] <Aryl>

[0161] In this invention, "aryl" refers to a group containing 6-120 carbon atoms (C6-C4). 120 Aryl group, preferably with 6-40 carbon atoms (C6-C4). 40 Aryl group, or 6-30 carbon atoms (C6-C4). 30 Aryl group, or 6-20 carbon atoms (C6-C4). 20 Aryl group, or 6-18 carbon atoms (C6-C4). 18 Aryl group, or 6-12 carbon atoms (C6-C4). 12 Aryl group, or 6-10 carbon atoms (C6-C4). 10Aromatic carbon ring systems consisting of monocyclic, bicyclic, tricyclic, tetracyclic, or pentacyclic rings (aryl groups). The term "aryl" may be used interchangeably with the term "aromatic ring." Examples of aryl groups may include phenyl, naphthyl, anthraceneyl, phenanthryl, pyrene, fluorenyl, spirodifluorenyl, etc.

[0162] <Miscellaneous Aromatics>

[0163] In this invention, "heteroaryl" refers to an aromatic monocyclic or polycyclic system containing a 5-120 member structure (5-120 member heteroaryl), preferably a 5-40 member structure (5-40 member heteroaryl), or a 5-30 member structure (5-30 member heteroaryl), or a 5-20 member structure (5-20 member heteroaryl), or a 5-18 member structure (5-18 member heteroaryl), or a 5-12 member structure (5-12 member heteroaryl), or a 5-10 member structure (5-10 member heteroaryl), or a 5-6 member structure (5-6 member heteroaryl), wherein at least one ring atom is a heteroatom and the remaining atoms are carbon, and the heteroatom is independently selected from N, O, S, Se or Te, and the number of heteroatoms is preferably 1, 2 or 3. The term "heteroaryl" can be used interchangeably with the term "heteroaryl ring". Examples of heteroaryl groups include carbazole, furanyl, thiophene, oxazolyl, thiazolyl, isoxazolyl, pyrrole, pyrazolyl, imidazole, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, pteridinyl, purine, indole, isoindole, indazole, benzofuranyl, benzothiophene, benzopyridyl, benzopyrimidinyl, benzopyrazinyl, and benzimidazolyl. wait.

[0164] Organic electroluminescent devices

[0165] The organic electroluminescent device of the present invention comprises, from bottom to top, a substrate, a first electrode, an organic functional material layer, and a second electrode, wherein the organic functional material layer comprises:

[0166] The hole transport region is located above the first electrode;

[0167] A light-emitting layer, located above the hole transport region, comprises a host material and a light-emitting material;

[0168] The electron transport region is located above the light-emitting layer;

[0169] The light-emitting layer comprises the compounds of the present invention.

[0170] Preferably, the luminescent material of the luminescent layer includes the compound of the present invention.

[0171] Preferably, the organic functional material layer further includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0172] Figure 2 This is a simplified structural diagram showing the organic electroluminescent device of the present invention. (See diagram below.) Figure 2 As shown, in the organic electroluminescent device of the present invention, for example, the anode 2, hole injection layer 3, hole transport layer 4, light-emitting layer 5, electron transport layer 6, electron injection layer 7 and cathode 8 are sequentially disposed on the substrate 1.

[0173] The organic electroluminescent device of the present invention is not limited to such a structure. For example, in this multilayer structure, some organic functional material layers may be omitted. For example, the hole injection layer 3 between the anode 2 and the hole transport layer 4, and the electron injection layer 7 between the electron transport layer 6 and the cathode 8 may be omitted, and the anode 2, the hole transport layer 4, the light-emitting layer 5, the electron transport layer 6 and the cathode 8 may be arranged sequentially on the substrate 1.

[0174] The organic electroluminescent device according to the present invention, except that the organic functional material layer comprises a compound represented by formula (G) above, can be manufactured using materials and methods known in the art. Furthermore, in the case where the organic electroluminescent device comprises multiple organic functional material layers, the organic functional material layers can be formed from the same substance or different substances.

[0175] For example, the organic electroluminescent device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. In this case, it can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or alloy thereof is deposited on the substrate to form an anode; then, an organic functional material layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer is formed on the anode; subsequently, a material suitable for use as a cathode is deposited on the organic material layer. However, the manufacturing method is not limited to this.

[0176] As an example, the first electrode described above is the anode and the second electrode is the cathode, or the first electrode described above is the cathode and the second electrode is the anode.

[0177] Preferably, the anode comprises a metal, a metal oxide, or a conductive polymer. For example, the work function of the anode may range from about 3.5 to 5.5 eV. Illustrative examples of conductive materials for the anode include carbon, aluminum, zinc, chromium, copper, zinc, silver, gold, other metals and their alloys; zinc oxide, steel oxide, tin oxide, steel tin oxide (ITO), steel zinc oxide and other similar metal oxides; and mixtures of oxides and metals, such as ZnO:Al and SnO2:Sb. Both transparent and opaque materials can be used as anode materials. For structures that emit light to the anode, a transparent anode can be formed. In this document, transparency means the degree to which light emitted from the organic material layer can pass through, and there are no particular limitations on the transmittance of light.

[0178] For example, when the organic light-emitting device of this specification is a top-emitting type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, not only transparent materials but also non-transparent materials with excellent light reflectivity can be used as anode materials. Alternatively, when the organic light-emitting device of this specification is a bottom-emitting type, and the anode is formed on the substrate before the organic material layer and the cathode are formed, a transparent material is required as the anode material, or the non-transparent material needs to be formed into a thin film that is thin enough to be transparent.

[0179] Preferably, regarding the cathode, a material with a low work function is preferred as the cathode material to facilitate electron injection. For example, in this specification, a material with a work function in the range of 2 eV to 5 eV can be used as the cathode material. The cathode may contain metals such as magnesium, calcium, sodium, potassium, titanium, steel, silane, lithium, rolled steel, aluminum, silver, tin, and lead or alloys thereof; materials with a multilayer structure, such as LiF / Al or LiO2 / Al, etc., but are not limited thereto.

[0180] The cathode can be formed using the same material as the anode. In this case, the cathode can be formed using the anode material as described above. Furthermore, the cathode or anode may contain a transparent material.

[0181] Depending on the materials used, the organic light-emitting device of the present invention can be a top-emitting, bottom-emitting, or side-emitting type. Preferably, the organic light-emitting device of the present invention includes a hole injection layer. This hole injection layer is preferably disposed between the anode and the light-emitting layer. The hole injection layer is formed from a hole injection material known to those skilled in the art. The hole injection material is a material that readily receives holes from the anode at low voltage, and the HOMO of the hole injection material is preferably located between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include, but are not limited to, metalloporphyrin-based organic materials, oligothiophene-based organic materials, aromatic amine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthoquinone-based conductive polymers, polyaniline-based conductive polymers, or polythiophene-based conductive polymers, etc.

[0182] Preferably, the organic light-emitting device of the present invention includes a hole transport layer. This hole transport layer is preferably disposed between the hole injection layer and the light-emitting layer, or between the anode and the light-emitting layer. The hole transport layer is formed of a hole transport material known to those skilled in the art. The hole transport material is preferably a material with high hole mobility, capable of transferring holes from the anode or hole injection layer to the light-emitting layer. Specific examples of hole transport materials include, but are not limited to, aromatic amine organic materials, conductive polymers, and block copolymers having bonding and non-bonding portions.

[0183] Preferably, the organic light-emitting device of the present invention further comprises an electron blocking layer. This electron blocking layer may preferably be disposed between the hole transport layer and the light-emitting layer, or between the hole injection layer and the light-emitting layer, or between the anode and the light-emitting layer. The electron blocking layer is formed of an electron blocking material known to those skilled in the art, such as TCTA.

[0184] Preferably, the organic light-emitting device of the present invention includes an electron injection layer. This electron injection layer is preferably disposed between the cathode and the light-emitting layer. The electron injection layer is formed from an electron injection material known to those skilled in the art. The electron injection layer can be formed using, for example, an electron-accepting organic compound. Here, as the electron-accepting organic compound, any known optional compound can be used without particular limitation. Such organic compounds can be: polycyclic compounds, such as p-terphenyl or tetraphenyl or derivatives thereof; polycyclic hydrocarbon compounds, such as naphthalene, tetraphenyl, perylene, hexabenzobenzene, chlorobenzene, senna, diphenylsenna, or phenanthrene, or derivatives thereof; or heterocyclic compounds, such as phenanthrene-rholine, phenanthridine, or derivatives thereof. Inorganic materials can also be used to form it, including but not limited to, such as magnesium, calcium, sodium, potassium, aluminum, silver, tin and lead or their alloys; LiF, LiO2, LiCoO2, NaCl, MgF2, CsF, CaF2, BaF2, NaF, RbF, CsCl, Ru2CO3, YbF3, etc.; and materials with multilayer structures, such as LiF / Al or LiO2 / Al, etc.

[0185] Preferably, the organic light-emitting device of the present invention includes an electron transport layer. This electron transport layer may preferably be disposed between the electron injection layer and the light-emitting layer, or between the cathode and the light-emitting layer. The electron transport layer is formed of an electron transport material known to those skilled in the art. An electron transport material is a material capable of readily receiving electrons from the cathode and transferring the received electrons to the light-emitting layer. Preferably, a material has a high electron mobility. Specific examples of electron transport materials include, but are not limited to, 8-hydroxyquinoline aluminum complexes; complexes containing 8-hydroxyquinoline aluminum; organic free radical compounds; and hydroxyflavonoid metal complexes; and TPBi.

[0186] Preferably, the organic light-emitting device of the present invention further includes a hole-blocking layer. This hole-blocking layer may preferably be placed between the electron transport layer and the light-emitting layer, or between the electron injection layer and the light-emitting layer, or between the cathode and the light-emitting layer. The hole-blocking layer is a layer that prevents injected holes from passing through the light-emitting layer to the cathode, and is typically formed under the same conditions as the hole injection layer. Specific examples include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc.

[0187] Preferably, the hole-blocking layer may be the same layer as the electron transport layer. Furthermore, preferably, the organic light-emitting device may also include a substrate. Specifically, in the organic light-emitting device, the anode or cathode may be provided on the substrate. There are no particular limitations on the substrate. The substrate may be a rigid substrate, such as a glass substrate, or a flexible substrate, such as a flexible thin-film glass substrate, a plastic substrate, or a film-shaped substrate.

[0188] The organic light-emitting device of the present invention can be manufactured using the same materials and methods known in the art. Specifically, the organic light-emitting device can be manufactured by the following steps: depositing a metal, conductive metal oxide, or alloy thereof onto a substrate using a physical vapor deposition (PVD) method (e.g., sputtering or electron beam evaporation) to form an anode; forming an organic material layer on the anode comprising a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, and an electron transport layer; and subsequently depositing a material thereon that can be used to form a cathode. Alternatively, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, one or more organic material layers, and an anode material onto a substrate. Furthermore, during the manufacture of the organic light-emitting device, in addition to physical vapor deposition, a solution coating method can be used to form the organic material layer of the organic light-emitting composite material of the present invention. As used in this specification, the term "solution coating method" refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, etc., but is not limited thereto.

[0189] There are no specific limitations on the thickness of each layer; those skilled in the art can determine it according to needs and specific circumstances. Preferably, the thicknesses of the light-emitting layer, hole injection layer, hole transport layer, electron blocking layer, electron transport layer, and electron injection layer are 0.5 to 150 nm, more preferably 1 to 100 nm. More preferably, the thickness of the light-emitting layer is 10 to 80 nm, more preferably 15 to 30 nm, for example 20 nm.

[0190] Example

[0191] The following detailed description, in conjunction with embodiments, illustrates the preparation methods of compounds represented by general formula (G) of the present invention and organic light-emitting devices comprising them. However, those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be construed as limiting the scope of the invention. Unless otherwise specified in the embodiments, conditions were performed under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0192] Example 1

[0193] Synthesis of intermediate H1:

[0194]

[0195] Under nitrogen atmosphere, 2.9 g (10 mmol) of methyl 2,6-dibromobenzoate, 1.7 g (10 mmol) of 5-chloro-2-methylphenylboronic acid, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of a mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The reaction solution was poured into approximately 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 1:1 (v / v)) to give 3.3 g of solid, yield 97.1%. MS (EI): m / z 337.97 [M] + Elemental analysis calculated value C 15 H 12 BrClO2 (%): C, 53.05; H, 3.56; Br, 23.53; Cl, ​​10.44; O, 9.42; Measured values: C, 59.05; H, 3.55; Br, 23.54; Cl, ​​10.44; O, 9.42.

[0196] Synthesis of intermediate J1:

[0197]

[0198] Under nitrogen atmosphere, 3.4 g (10 mmol) of intermediate H1, 1.63 g (16.94 mmol) of methanesulfonic acid, and 30 mL of toluene were added sequentially to a clean 100 mL three-necked flask. The system was heated to 110 °C and reacted overnight. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane = 4:1 (v / v)) to give 3.0 g of a yellow solid, with a yield of 97.7%. MS (EI): m / z 305.94 [M] + Elemental analysis calculated value C 14 H8BrClO (%): C, 54.67; H, 2.62; Br, 25.98; Cl, ​​11.53; O, 5.20; Measured values: C, 54.64; H, 2.62; Br, 25.94; Cl, ​​11.51; O, 5.21.

[0199] Synthesis of intermediate L1:

[0200]

[0201] Under nitrogen atmosphere, 3.1 g (10 mmol) of intermediate J1, 7.7 g (10 mmol) of BNN-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 8.5 g of a yellow solid, with a yield of 98.1%. MS (EI): m / z 866.42 [M] + Elemental analysis calculated value C 60 H 56 BClN2O (%): C, 83.08; H, 6.51; B, 1.25; Cl, ​​4.09; N, 3.23; O, 1.84; Measured values: C, 83.09; H, 6.56; B, 1.22; Cl, ​​4.07; N, 3.23; O, 1.83.

[0202] Synthesis of intermediates L2 to L32:

[0203] Following the synthesis method of intermediate L1, the following intermediates L2 to L32 were synthesized:

[0204]

[0205]

[0206] MS[M] of intermediates L2 to L32 + The values ​​are shown in Table 1 below:

[0207] Table 1

[0208] Intermediate number <![CDATA[MS[M] + ]]> Intermediate number <![CDATA[MS[M] + ]]> L2 737.32 L14 976.31 L3 1312.69 L15 1398.37 L4 674.16 L16 428.10 L5 706.11 L17 478.11 L6 802.0 L18 480.13 L7 770.29 L19 630.15 L8 698.16 L20 730.18 L9 715.12 L28 646.98 L10 523.10 L29 646.98 L11 1758.96 L30 723.08 L12 1081.49 L31 867.38 L13 549.08 L32 814.27

[0209] Synthesis of intermediate M1:

[0210]

[0211] Under nitrogen atmosphere, 8.7 g (10 mmol) of intermediate L1, 4.4 g (10 mmol) of TRZ-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (dioxane:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 100 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 11.0 g of a yellow solid, yield 96.5%. MS (EI): m / z 1139.51 [M] + Elemental analysis calculated value C 81 H 70 BN5O (%): C, 85.32; H, 6.19; B, 0.95; N, 6.14; O, 1.40; Measured values: C, 85.34; H, 6.19; B, 0.97; N, 6.12; O, 1.40.

[0212] Synthesis of intermediates M2 to M39:

[0213] Following the synthesis method of intermediate M1, the following intermediates M2 to M39 were synthesized:

[0214]

[0215]

[0216] MS[M] of intermediate compounds M2 to M39 + The values ​​are shown in Table 2 below:

[0217] Table 2

[0218]

[0219]

[0220] Synthesis of compound BNN-1:

[0221]

[0222] Under nitrogen protection, 3.6 g (11 mmol) of 2-bromotriphenylamine was placed in a 250 mL two-necked flask, dissolved in 100 mL of anhydrous tetrahydrofuran, and then placed at -78 °C. 4.58 mL (11 mmol) of a 2.40 mol / L n-butyllithium solution was added dropwise. After stirring at -78 °C for 1 hour, 11.4 g (10 mmol) of intermediate M1 was added, and the mixture was stirred overnight. The mixture was then quenched with 10 mL of distilled water. The tetrahydrofuran was removed from the reaction solution under reduced pressure, and the solution was extracted three times with 40 mL of ethyl acetate. The organic phase was collected, the ethyl acetate was removed under reduced pressure, and the mixture was recrystallized with ethanol. After filtration and drying, the solid was placed in a 100 mL flask, 20 mL of acetic acid was added, and the mixture was stirred for 10 minutes. Then, 3 mL of concentrated hydrochloric acid was added, and the mixture was heated to 110 °C and refluxed for 3 hours. After the reaction was complete, the temperature was lowered to room temperature, and the reaction solution was poured into 500 mL of ice water. The product precipitated, and after filtration, it was subjected to silica gel column chromatography using a mixture of dichloromethane and petroleum ether as eluent to obtain compound BNN-1 (13.0 g, yield approximately 95.1%). MS (EI): m / z 1366.68 [M] + Elemental analysis calculated value C 99 H 83 BN6 (%): C, 86.95; H, 6.12; B, 0.79; N, 6.15; Measured values: C, 86.97; H, 6.11; B, 0.79; N, 6.14. 1 The H NMR spectrum is shown in [reference]. Figure 13 .

[0223] Synthesis of compounds BNN-19 to BNO-64:

[0224] Following the synthetic method for compound BNN-1, the following compounds BNN-19 to BNO-64 were synthesized:

[0225]

[0226]

[0227]

[0228]

[0229] MS [M] of compounds BNN-19 to BNO-64 + The values ​​are shown in Table 3 below for compound BNO-4. 1 The H NMR spectrum is shown in [reference]. Figure 14 .

[0230] Table 3

[0231]

[0232] Example 2

[0233] Synthesis of intermediate H2:

[0234]

[0235] Under nitrogen atmosphere, 2.9 g (10 mmol) of methyl 2,6-dibromobenzoate, 2.3 g (10 mmol) of (5-chloro-2-(trimethylsilyl)phenyl)boronic acid, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetra(triphenylphosphine)palladium, and 100 mL of a mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The reaction solution was poured into approximately 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 1:1 (v / v)) to give 3.8 g of solid, yield 95.5%. MS(EI): m / z 395.99 [M] + Elemental analysis calculated value C 17 H 18 BrClO2Si (%): C, 51.33; H, 4.56; Br, 20.09; Cl, ​​8.91; O, 8.04; Si, 7.06; Measured values: C, 51.33; H, 4.56; Br, 20.09; Cl, ​​8.92; O, 8.04; Si, 7.05.

[0236] Synthesis of intermediate J2:

[0237]

[0238] Under nitrogen atmosphere, 4.0 g (10 mmol) of intermediate H2, 1.63 g (16.94 mmol) of methanesulfonic acid, and 30 mL of toluene were added sequentially to a clean 100 mL three-necked flask. The system was heated to 110 °C and reacted overnight. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The crude product was then concentrated by vacuum distillation. Under nitrogen atmosphere, the crude product, 5.2 g (20 mmol) of tetrabutylammonium fluoride, and 50 mL of tetrahydrofuran were added sequentially to a clean 100 mL three-necked flask. The system was heated to 60 °C and reacted for 3 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The reaction solution was poured into approximately 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether:dichloromethane = 1:1 (v / v)) to give 2.8 g of solid, with a yield of 95.9%. MS(EI): m / z 291.93[M]+. Elemental analysis calculated C. 13 H6BrClO (%): C, 53.19; H, 2.06; Br, 27.22; Cl, ​​12.08; O, 5.45; Measured values: C, 53.19; H, 2.08; Br, 27.22; Cl, ​​12.08; O, 5.43.

[0239] Synthesis of intermediate L21:

[0240]

[0241] Under nitrogen atmosphere, 2.9 g (10 mmol) of intermediate J2, 7.7 g (10 mmol) of BNN-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 8.5 g of a yellow solid, with a yield of 99.6%. MS (EI): m / z 853.35 [M] + Elemental analysis calculated value C 59 H 54 BClN2O (%): C, 83.04; H, 6.38; B, 1.27; Cl, ​​4.15; N, 3.28; O, 1.87; Measured values: C, 83.04; H, 6.39; B, 1.28; Cl, ​​4.15; N, 3.28; O, 1.84.

[0242] Synthesis of intermediates L22 to L39:

[0243] Following the synthesis method of intermediate L21, intermediates L22 to L39 were synthesized as follows:

[0244]

[0245] MS[M] of intermediates L22 to L39 + The values ​​are shown in Table 4 below:

[0246] Table 4

[0247] Compound numbering <![CDATA[MS[M] + ]]> Compound numbering <![CDATA[MS[M] + ]]> L22 723.31 L35 853.85 L23 1298.67 L36 724.15 L24 660.14 L37 800.25 L33 632.95 L38 800.25 L34 709.05 L39 800.25

[0248] Synthesis of intermediate M27:

[0249]

[0250] Under nitrogen atmosphere, 8.5 g (10 mmol) of intermediate L21, 4.4 g (10 mmol) of TRZ-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (dioxane:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 100 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 11.0 g of a yellow solid, with a yield of 97.7%. MS (EI): m / z 1125.55 [M] + Elemental analysis calculated value C 80 H 68 BN5O (%): C, 85.32; H, 6.09; B, 0.96; N, 6.22; O, 1.42; Measured values: C, 85.32; H, 6.07; B, 0.96; N, 6.24; O, 1.42.

[0251] Synthesis of intermediates M28 to M47:

[0252] Following the synthesis method of intermediate M27, intermediates M28 to M47 were synthesized as follows:

[0253]

[0254] MS [M] of intermediate compounds M28 to M47 + The values ​​are shown in Table 5 below:

[0255] Table 5

[0256]

[0257] Synthesis of compound BNN-39:

[0258]

[0259] Under nitrogen protection, 3.6 g (11 mmol) of 2-bromotriphenylamine was placed in a 250 mL two-necked flask, dissolved in 100 mL of anhydrous tetrahydrofuran, and then placed at -78 °C. 4.58 mL (11 mmol) of a 2.40 mol / L n-butyllithium solution was added dropwise, and the mixture was stirred at -78 °C for 1 hour. Then, 11.3 g (10 mmol) of intermediate M27 was added, and the mixture was stirred overnight. The mixture was then quenched with 10 mL of distilled water. The tetrahydrofuran was removed from the reaction solution under reduced pressure, and the mixture was extracted three times with 40 mL of ethyl acetate. The organic phase was collected, the ethyl acetate was removed under reduced pressure, and the mixture was recrystallized with ethanol. The solid was filtered, dried, and placed in a 100 mL flask. 20 mL of acetic acid was added, and the mixture was stirred for 10 minutes. 3 mL of concentrated hydrochloric acid was then added, and the mixture was heated to 110 °C and refluxed for 3 hours. After the reaction was complete, the temperature was lowered to room temperature, and the reaction solution was poured into 500 mL of ice water. The product precipitated, and after filtration, it was eluented with a mixture of dichloromethane and petroleum ether and then subjected to silica gel column chromatography to obtain compound BNN-39 (13.0 g, yield approximately 96.0%). MS (EI): m / z 1352.66 [M] + Elemental analysis calculated value C 98 H 81 BN6 (%): C, 86.96; H, 6.03; B, 0.80; N, 6.21; Measured values: C, 86.99; H, 6.01; B, 0.80; N, 6.20.

[0260] Synthesis of compounds BNO-44 to BNO-63:

[0261] Following the synthetic method for BNN-39, compounds BNO-44 to BNO-63 were synthesized:

[0262]

[0263]

[0264] MS [M] of compounds BNO-44 to BNO-63 + The values ​​are shown in Table 6 below:

[0265] Table 6

[0266]

[0267] Example 3

[0268] Synthesis of intermediate H3:

[0269]

[0270] Under nitrogen atmosphere, 2.3 g (10 mmol) of methyl 2-bromo-6-fluorobenzoate, 7.5 g (20 mmol) of anhydrous cesium carbonate, 1.4 g (10 mmol) of 5-chloro-2-methylphenol, 115.4 mg (20 mmol) of cesium carbonate, and 100 mL of N,N-dimethylformamide were added sequentially to a clean 250 mL three-necked flask. The system was heated to 150 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The reaction solution was poured into approximately 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether:dichloromethane = 1:1 (v / v)) to give 3.1 g of solid, yield 87.3%. MS (EI): m / z 353.97 [M] + Elemental analysis calculated value C 15 H 12 BrClO3 (%): C, 50.66; H, 3.40; Br, 22.47; Cl, ​​9.97; O, 13.50; Measured values: C, 50.66; H, 3.40; Br, 22.47; Cl, ​​9.97; O, 13.50.

[0271] Synthesis of intermediate J3:

[0272]

[0273] Under nitrogen atmosphere, 3.6 g (10 mmol) of intermediate H3, 1.63 g (16.94 mmol) of methanesulfonic acid, and 30 mL of toluene were added sequentially to a clean 100 mL three-necked flask. The system was heated to 110 °C and reacted overnight. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane = 4:1 (v / v)) to give 3.0 g of a yellow solid, yield 92.6%. MS (EI): m / z 321.94 [M] + Elemental analysis calculated value C 14 H8BrClO2 (%): C, 51.97; H, 2.49; Br, 24.69; Cl, ​​10.96; O, 9.89; Measured values: C, 51.97; H, 2.48; Br, 24.69; Cl, ​​10.97; O, 9.89.

[0274] Synthesis of intermediate L25:

[0275]

[0276] Under nitrogen atmosphere, 2.9 g (10 mmol) of intermediate J3, 7.7 g (10 mmol) of BNN-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 8.0 g of a yellow solid, with a yield of 90.1%. MS (EI): m / z 882.41 [M] + Elemental analysis calculated value C 60 H 56 BClN2O2 (%): C, 81.58; H, 6.39; B, 1.22; Cl, ​​4.01; N, 3.17; O, 3.62; Measured values: C, 81.57; H, 6.39; B, 1.22; Cl, ​​4.00; N, 3.15; O, 3.65.

[0277] Synthesis of intermediate L26:

[0278]

[0279] The synthesis method for intermediate L26 is the same as that for intermediate L25. The MS[M] of intermediate L26... + Value: 753.32.

[0280] Synthesis of intermediate M31:

[0281]

[0282] Under nitrogen atmosphere, 8.8 g (10 mmol) of intermediate L25, 4.4 g (10 mmol) of TRZ-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (dioxane:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 100 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 11.0 g of a yellow solid, with a yield of 95.2%. MS (EI): m / z 1155.56 [M] + Elemental analysis calculated value C 81 H 70BN5O2 (%): C, 84.14; H, 6.10; B, 0.93; N, 6.06; O, 2.77; Measured values: C, 84.12; H, 6.10; B, 0.93; N, 6.06; O, 2.79.

[0283] Synthesis of intermediates M32 and M33:

[0284] Following the synthesis method of intermediate M31, intermediates M32 and M33 were synthesized as follows:

[0285]

[0286] MS[M] of intermediates M32 and M33 + The values ​​are shown in Table 7 below:

[0287] Table 7

[0288] Intermediate number <![CDATA[MS[M] + ]]> M32 1268.53 M33 1042.50

[0289] Synthesis of compound BNN-3:

[0290]

[0291] Under nitrogen protection, 3.6 g (11 mmol) of 2-bromotriphenylamine was placed in a 250 mL two-necked flask, dissolved in 100 mL of anhydrous tetrahydrofuran, and then placed at -78 °C. 4.58 mL (11 mmol) of a 2.40 mol / L n-butyllithium solution was added dropwise. After stirring at -78 °C for 1 hour, 11.6 g (10 mmol) of intermediate M31 was added, and the mixture was stirred overnight. The mixture was then quenched with 10 mL of distilled water. The tetrahydrofuran was removed from the reaction solution under reduced pressure, and the mixture was extracted three times with 40 mL of ethyl acetate. The organic phase was collected, the ethyl acetate was removed under reduced pressure, and the mixture was recrystallized with ethanol. After filtration and drying, the solid was placed in a 100 mL flask, 20 mL of acetic acid was added, and the mixture was stirred for 10 minutes. Then, 3 mL of concentrated hydrochloric acid was added, and the mixture was heated to 110 °C and refluxed for 3 hours. After the reaction was complete, the temperature was lowered to room temperature, and the reaction solution was poured into 500 mL of ice water. The product precipitated, and after filtration, it was eluented with a mixture of dichloromethane and petroleum ether and then subjected to silica gel column chromatography to obtain compound BNN-3 (13.0 g, yield approximately 92.9%). MS (EI): m / z 1398.70 [M] + Elemental analysis calculated value C 100 H 87 BN6O (%): C, 85.81; H, 6.27; B, 0.77; N, 6.00; O, 1.14; Measured values: C, 85.80; H, 6.25; B, 0.77; N, 6.00; O, 1.17.

[0292] Synthesis of compounds BNN-21 to BNO-37:

[0293] Following the synthetic method for compound BNN-3, compounds BNN-21 to BNO-37 were synthesized:

[0294]

[0295] MS [M] of compounds BNN-21 to BNO-37 + The values ​​are shown in Table 8 below:

[0296] Table 8

[0297] Compound numbering <![CDATA[MS[M] + ]]> BNN-21 1626.80 BNN-22 1412.68 BNN-35 1509.62 BNO-9 1309.64 BNO-37 1251.56

[0298] Example 4

[0299] Synthesis of intermediate H4

[0300]

[0301] Under nitrogen atmosphere, 3.4 g (10 mmol) of methyl 2,6-dibromobenzoate, 2.1 g (10 mmol) of 5-chloro-2-tert-butylphenylboronic acid, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of a mixed solvent (tetrahydrofuran:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 65 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The reaction solution was poured into approximately 200 mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 1:1 (v / v)) to give 3.7 g of solid, yield 97.4%. MS (EI): m / z 380.02 [M] + Elemental analysis calculated value C 18 H 18 BrClO2 (%): C, 56.64; H, 4.75; Br, 20.93; Cl, ​​9.29; O, 8.38; Measured values: C, 56.63; H, 4.75; Br, 20.93; Cl, ​​9.29; O, 8.39.

[0302] Synthesis of intermediate J4:

[0303]

[0304] Under nitrogen atmosphere, 4.0 g (10 mmol) of intermediate H4, 1.63 g (16.94 mmol) of methanesulfonic acid, and 30 mL of toluene were added sequentially to a clean 100 mL three-necked flask. The system was heated to 110 °C and reacted overnight. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent: petroleum ether: dichloromethane = 4:1 (v / v)) to give 3.2 g of a yellow solid, yield 91.4%. MS (EI): m / z 347.99 [M] + Elemental analysis calculated value C 17 H 14 BrClO (%): C, 58.40; H, 4.04; Br, 22.85; Cl, ​​10.14; O, 4.58; Measured values: C, 58.41; H, 4.04; Br, 22.85; Cl, ​​10.13; O, 4.58.

[0305] Synthesis of intermediate L27:

[0306]

[0307] Under nitrogen atmosphere, 3.5 g (10 mmol) of intermediate J4, 7.7 g (10 mmol) of BNN-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (dioxane:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 100 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to give 8.5 g of a yellow solid, with a yield of 93.6%. MS (EI): m / z 908.46 [M] + Elemental analysis calculated value C 63 H 62 BClN2O (%): C, 83.20; H, 6.87; B, 1.19; Cl, ​​3.90; N, 3.08; O, 1.76; Measured values: C, 83.21; H, 6.87; B, 1.19; Cl, ​​3.90; N, 3.07; O, 1.76.

[0308] Synthesis of intermediate M34:

[0309]

[0310] Under nitrogen atmosphere, 9.1 g (10 mmol) of intermediate L27, 4.4 g (10 mmol) of TRZ-bpin, 2.72 g (20 mmol) of anhydrous potassium carbonate, 115.4 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium, and 100 mL of mixed solvent (dioxane:water = 5:1 (v / v)) were added sequentially to a clean 250 mL three-necked flask. The system was heated to 100 °C and reacted for 12 hours. After the reaction was complete, heating was stopped, and the reaction system was allowed to cool to room temperature. The mixture was then concentrated by vacuum distillation and further purified by column chromatography (350 mesh silica gel, eluent:petroleum ether:dichloromethane = 3:1 (v / v)) to obtain 11.5 g of yellow solid, yield 97.3%. MS (EI): m / z 1181.61 [M] + Elemental analysis calculated value C 84 H 76 BN5O (%): C, 85.33; H, 6.48; B, 0.91; N, 5.92; O, 1.35; Measured values: C, 85.33; H, 6.49; B, 0.91; N, 5.92; O, 1.34.

[0311] Synthesis of compound BNN-7:

[0312]

[0313] Under nitrogen protection, 3.6 g (11 mmol) of 2-bromotriphenylamine was placed in a 250 mL two-necked flask, dissolved in 100 mL of anhydrous tetrahydrofuran, and then placed at -78 °C. 4.58 mL (11 mmol) of a 2.40 mol / L n-butyllithium solution was added dropwise, and the mixture was stirred at -78 °C for 1 hour. Then, 11.8 g (10 mmol) of intermediate M34 was added, and the mixture was stirred overnight. The mixture was then quenched with 10 mL of distilled water. The tetrahydrofuran was removed from the reaction solution under reduced pressure, and the mixture was extracted three times with 40 mL of ethyl acetate. The organic phase was collected, the ethyl acetate was removed under reduced pressure, and the mixture was recrystallized with ethanol. The solid was filtered, dried, and placed in a 100 mL flask. 20 mL of acetic acid was added, and the mixture was stirred for 10 minutes. 3 mL of concentrated hydrochloric acid was then added, and the mixture was heated to 110 °C and refluxed for 3 hours. After the reaction was complete, the temperature was lowered to room temperature, and the reaction solution was poured into 500 mL of ice water. The product precipitated, and after filtration, it was eluented with a mixture of dichloromethane and petroleum ether and then subjected to silica gel column chromatography to obtain compound BNN-7 (13.7 g, yield approximately 97.2%). MS (EI): m / z 1408.72 [M] + Elemental analysis calculated value C 102 H 89 BN6 (%): C, 86.91; H, 6.36; B, 0.77; N, 5.96; Measured values: C, 86.91; H, 6.34; B, 0.79; N, 5.96.

[0314] The proton NMR spectral data of some compounds of this invention are shown in Table 9:

[0315] Table 9

[0316]

[0317] Example 5: Fabrication of Organic Electroluminescent Device 1 (Organic EL Device 1)

[0318] Hole injection layer (HIL) 3, hole transport layer (HTL) 4, electron blocking layer (EBL) 5, light-emitting layer (EML) 6, hole blocking layer (HBL) 7, electron transport layer (ETL) 8, electron injection layer (EIL) 9, and cathode 10 are sequentially formed on the transparent anode 2 on the pre-fabricated glass substrate 1 to prepare a structure as shown in the figure. Figure 2 The organic electroluminescent device shown.

[0319] Specifically, a glass substrate with a 100 nm thick ITO film was ultrasonically treated three times in a commercial cleaning solution, ultrasonically treated three times in deionized water, and sequentially cleaned three times in ethanol and acetone. It was then baked in a clean environment for six hours, irradiated with ultraviolet light, cleaned with ozone, and bombarded with a low-energy cation beam. The glass substrate was then placed in a vacuum chamber and evacuated to a vacuum level less than 1 × 10⁻⁶. -5 Pa. Then on the glass substrate, with A HAT-CN organic layer was deposited at a evaporation rate of [value missing], forming a hole injection layer with a thickness of 10 nm. On the hole injection layer, [details missing]. A BCFN organic layer was deposited at a high evaporation rate to form a hole transport layer with a thickness of 30 nm. On the hole transport layer, at... A Tris-PCz organic layer was deposited at a deposition rate of [value missing] to form an electron blocking layer with a thickness of 20 nm. On the electron blocking layer, the deposition rate of SiCzCz, the host material, was [value missing]. The evaporation rate of compound BNN-1, used as a luminescent material, is: Dual-source co-evaporation was performed at a high evaporation rate to form a 20 nm thick layer as the light-emitting layer, with the compound BNN-1 doped at a weight ratio of 10 wt%. On the light-emitting layer, [the following text appears to be incomplete and requires further context: "...with..."] A CF3-TRZ organic layer was deposited at a evaporation rate of [value missing], forming a hole-blocking layer with a thickness of 10 nm. On the electron-blocking layer, [details missing]. A BPPB organic layer was deposited at a high evaporation rate to form an electron transport layer with a thickness of 40 nm. On the electron transport layer, at... A BPPB organic layer was deposited at a evaporation rate of [value missing], forming an electron transport layer with a thickness of 40 nm. 8-hydroxyquinoline-lithium (Liq) was deposited at a high evaporation rate to form a 2 nm thick layer as an electron injection layer. Finally, 8-hydroxyquinoline-lithium (Liq) was deposited at a high evaporation rate to form a 2 nm thick layer. Aluminum is deposited at the above evaporation rate to form a cathode with a film thickness of 100 nm.

[0320] Examples 6-54: Fabrication of Organic EL Devices 2-50

[0321] Organic EL devices 2 to 50 were fabricated under the same conditions as organic EL device 1, except that the compounds in each layer of Example 5 were replaced with the compounds in Table 10 below.

[0322] Examples 55 and 56: Fabrication of Organic EL Devices 51 and 52

[0323] The device was fabricated in the same manner as in Example 5, except that the light-emitting layer used only BNN-1 and BNO-4 materials.

[0324] Comparative Examples 1 and 2: Fabrication of Comparative Devices 1 and 2

[0325] The device was fabricated in the same manner as in Example 5, except that the light-emitting material of the light-emitting layer was BNN and DM-B, respectively, and the thickness of the light-emitting layer was reduced to 5 nm.

[0326] Comparative Examples 3 and 4: Fabrication of Comparative Devices 3 and 4

[0327] The device was fabricated in the same manner as in Example 5, except that the light-emitting material of the light-emitting layer was BNO or DM-C, and the hole injection layer, hole transport layer, and host material were HIL1, HTL1, and BH2, respectively.

[0328] Comparative Example 5: Fabrication of Comparative Device 5

[0329] The device was fabricated in the same manner as in Example 5, except that the luminescent material of the luminescent layer was co-doped with BNN and DM-B materials, respectively.

[0330] Comparative Example 6: Fabrication of Comparative Device 6

[0331] The device was fabricated in the same manner as in Example 5, except that the light-emitting material of the light-emitting layer was co-doped with BNO and DM-C materials, and the hole injection layer, hole transport layer and host material were HIL1, HTL1 and BH2, respectively.

[0332] Comparative Example 7: Fabrication of Comparative Device 7

[0333] The device was fabricated in the same manner as in Example 5, except that the light-emitting material of the light-emitting layer was co-doped with SSBD-21 material, and the hole injection layer, hole transport layer and host material were HIL1, HTL1 and BH2, respectively.

[0334] Table 10

[0335]

[0336]

[0337]

[0338]

[0339]

[0340] Note: In Comparative Example 5, the total doping amount of DM-B and BNN was 10 wt%, the doping amounts of DM-B and BNN were 5.3 wt% and 4.7 wt%, respectively, and the molar ratio of DM-B to BNN was 1:1; In Comparative Example 6, the total doping amount of DM-C and BNO was 10 wt%, the doping amounts of DM-C and BNO were 6.1 wt% and 3.9 wt%, respectively, and the molar ratio of DM-C to BNO was 1:1.

[0341] The structures of the compounds involved in the examples are as follows:

[0342]

[0343]

[0344]

[0345] The luminescence characteristics of organic EL devices 1-52 fabricated in Examples 5-56 and organic EL comparison devices 1-7 fabricated in Comparative Examples 1-7 were measured under ambient atmospheric conditions when a DC voltage was applied. The measurement results are shown in Table 11. The current-luminosity-voltage characteristics of the devices were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes. The electroluminescence spectra were measured using a Photoresearch PR655 spectrometer. The external quantum efficiency of the devices was calculated using the method described in Adv. Mater., 2003, 15, 1043-1048.

[0346] Table 11

[0347]

[0348]

[0349] The current-luminosity-voltage characteristics of the device were measured using a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode. The electroluminescence spectrum was measured using a Photo Research PR655 spectrometer. The external quantum efficiency of the device was calculated using the method described in Adv. Mater. 2003, 15, 1043-1048.

[0350] As shown in Table 11, comparative devices 1 and 3 exhibit narrow-band emission, but have low external quantum efficiency, severe efficiency roll-off, and short operating lifetime. Comparative devices 2 and 4 exhibit high external quantum efficiency, slight efficiency roll-off, and long operating lifetime, but have a wide full width at half maximum (FWHM), which severely affects color purity. Both types of comparative devices have significant shortcomings that directly impact their commercial application. However, devices 1-50 not only exhibit narrow-band emission with emission wavelengths essentially consistent with the emitting unit, but also demonstrate high external quantum efficiency, slight efficiency roll-off, and long operating lifetime, highlighting the rationality of the luminescent material design in this invention and achieving the material design objectives, which is beneficial for its industrial production and application. The luminescent layers of devices 51 and 52 are formed solely by vapor deposition of the luminescent material, and the thickness is reduced to 5 nm, which not only reduces the manufacturing difficulty but also saves materials, while having minimal impact on the device's photoelectric performance. Furthermore, the light-emitting layers of the comparative devices 5 and 6 are formed by ternary co-evaporation of the host material, sensitizer material, and light-emitting material. The preparation process is complex and the cost increases sharply. At the same time, since the sensitizer material and MR light-emitting material are doped in the host material, the energy transfer is insufficient, which inevitably leads to spectral broadening. In addition, the triplet excitons are not fully consumed, which reduces the external quantum efficiency of the device and shortens the device's operating life.

[0351] Comparative Example 7 uses SSBD-21, a self-sensitized narrow-band blue light-emitting material disclosed in CN116675712A, in which the emitting unit and sensitizing unit are fixed at both ends of a helical ring structure. However, the emitting unit and sensitizing unit of SSBD-21 are constrained by the orthogonal conformation of the helical ring structure, resulting in an unfavorable dipole-dipole orientation between them, leading to... The low energy transfer efficiency causes the sensitization unit to also participate in luminescence, making it difficult for the obtained electroluminescence spectrum to match the emission spectrum of the luminescent unit, thus limiting the fabrication of high-color-purity devices. More importantly, excitons that are not transferred to the luminescent molecules are extremely detrimental to the stability of the device, severely shortening its operating life.

[0352] In summary, the material of this invention has excellent photoelectric properties and can be used as a luminescent material for the organic emitting layer of organic electroluminescent devices. It can also simplify the manufacturing process of organic electroluminescent devices and ultimately realize organic light-emitting diode devices with high external quantum efficiency, low efficiency roll-off, long lifetime, and narrow-band emission.

[0353] Experimental Example 1

[0354] Thermogravimetric differential thermal analysis (TG-DTA) was performed by a TGA-Q5000IR (TA Instruments, USA) at 10 °C / min under a nitrogen atmosphere. -1 The heating rate was determined. Absolute fluorescence quantum efficiency was measured under a nitrogen atmosphere using a Quantaurus QY measurement system (C11347-11, Hamamatsu Photonics). Specific data for the materials used in the measurement examples, as well as the thermal decomposition temperatures and fluorescence quantum efficiencies of BNN, DM-C, BNO, DM-C, and SSBD, are shown in Table 12.

[0355] Table 12

[0356]

[0357]

[0358] As shown in Table 12, the self-sensitized thermally activated delayed fluorescence materials of the present invention exhibit a fluorescence quantum efficiency of >90% and excellent thermal stability. In particular, the fluorescence quantum efficiency of the self-sensitized thermally activated delayed fluorescence materials of the present invention (such as BNN-1 and BNO-4) is closer to that of the luminescent units (BNN and BNO), and significantly higher than that of the TADF-sensitized units.

[0359] Experimental Example 2

[0360] The UV absorption spectrum of the self-sensitized thermally activated delayed fluorescence material of the present invention in toluene was tested, wherein... Figure 3 The images show the UV absorption spectra of materials BNO, DM-C, and BNO-4 measured in toluene. Figure 4 This is the ultraviolet absorption spectrum of material BNN-1 measured in toluene.

[0361] Depend on Figure 3 It can be seen that the ultraviolet absorption spectrum of BNO-4 is basically the same as that of BNO and DM-C. The peak at 450nm to 460nm is slightly red-shifted, which is attributed to the slight influence of the emitting unit on the base, which is consistent with the red shift of the fluorescence spectrum. Figure 4 The self-sensitized thermally activated delayed fluorescent material BNN-1 exhibits obvious absorption peaks of luminescent units.

[0362] Experimental Example 3

[0363] The fluorescence spectrum of the self-sensitized thermally activated delayed fluorescent material of the present invention in toluene was tested, wherein... Figure 5 The following are fluorescence spectra of materials Perylene-1, NPO-4, BNN-26, and BNONO-1 measured in toluene. Figure 6 The fluorescence spectra of materials BNOCz-1, NAJCz-5, BPX-7, and BNO-23 measured in toluene are shown.

[0364] Depend on Figure 5 , 6 It can be seen that the fluorescence spectrum of the thermally activated delayed fluorescence material of the present invention basically reflects the fluorescence of the luminescent unit, and maintains narrow band luminescence in toluene solution.

[0365] Experiment Example 4

[0366] The fluorescence spectra of the self-sensitized thermally activated delayed fluorescent material of the present invention and BNO and DM-C in different solvents (cyclohexane, toluene, chloroform, N,N-dimethylformamide) were tested. Figure 7 The following are fluorescence spectra of material BNO-4 in different solvents. Figure 8 The following are fluorescence spectra of material BNN-1 in different solvents. Figure 9 The following are fluorescence spectra of materials BNO, DM-C, and BNO-4 measured in toluene. Figure 10 The fluorescence spectra of materials BNO, DM-C, and BNO-4 measured in N,N-dimethylformamide are shown.

[0367] Depend on Figure 7 It is known that BNO-4 gradually exhibits fluorescence spectra of the sensitizing unit with increasing solvent polarity. This is attributed to the fact that, with increasing solvent polarity, the energy levels of the lowest excited singlet states of the sensitizing and luminescent units gradually approach each other. Figure 8 It can be seen that the solvation effect of BNN-1 is very weak, which is attributed to the fact that the lowest excitation singlet state of the luminescent unit is always smaller than that of the lowest excitation singlet state of the sensitizing unit.

[0368] Depend on Figure 9 It can be seen that in toluene solution, the fluorescence spectra of BNO-4 and BNO are basically the same, with only a slight red shift. From... Figure 10 It can be seen that in N,N-dimethylformamide solution, the fluorescence spectrum of BNO-4 shows some peaks consistent with the fluorescence spectrum of DM-C, indicating that the energy levels of the lowest excited singlet state of the sensitizing unit and the luminescent unit gradually approach each other, and some peaks of the fluorescence spectrum of BNO-4 show only a slight red shift compared with the fluorescence spectrum of BNO.

[0369] Experimental Example 5

[0370] The transient photoluminescence decay spectra of the self-sensitized thermally activated delayed fluorescent material of the present invention and BNO and BNN in toluene were tested, wherein... Figure 11 The transient photoluminescence decay spectra of materials BNO-4 and BNO in toluene are shown. Figure 12 The transient photoluminescence decay spectra of materials BNN-1 and BNN in toluene are shown.

[0371] Depend on Figure 11 , 12 It can be seen that BNO-4 and BNN-1 exhibit more delayed components than BNO and BNN, respectively, proving that the sensitization unit carried out energy transfer and fully consumed the triplet exciton.

[0372] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0373] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A compound having the structure shown in formula (G): in, X represents -C(R a )(R b )-, -NR a -, -BiR a -, -BR a -, -Si(R a )(R b )-, -Ge(R a )(R b )-, -O-, -S-, -Se-, -Te-, -S(=O)2-, -C(=O)-、-P(=O)(R a - or single bond; F1 and F2 each independently represent -C(R) a (R) b )-、-NR a -、-BiR a -、-BR a -、-Si(R a (R) b )-、-Ge(R a (R) b )-, -O-, -S-, -Se-, -Te-, -S(=O)2-, -C(=O)-, -P(=O)(R a - or a single bond or none at all; when at least one of F1 and F2 is absent, the carbon atom attached to it is capped with hydrogen; Each R a R b Each independently represents hydrogen, deuterium, halogen atoms, and C1-C atoms. 15 Alkyl or C6-C 18 Aryl; R1-R 15 Each independently represents hydrogen, deuterium, halogen atom, cyano, nitro, hydroxyl, amino, mercapto, optionally with one or more R groups. c Replacement C1-C 15 Alkyl, optionally with one or more R c Replacement C1-C 15 Halogenated alkyl, optionally with one or more R c Replacement C1-C 15 Alkoxy, optionally with one or more R c Replacement -S(C1-C) 15 Alkyl), optionally with one or more R c Substituted -Si(R) 16 (R) 17 (R) 18 ), can be arbitrarily controlled by one or more R c Replacement -N(R) 16 (R) 17 ), can be arbitrarily controlled by one or more R c Replacement C6-C 18 aryl or optionally substituted with one or more R c Substituted 5-18 heteroaryl groups; Each R 16 R 17 R 18 Each independently represents hydrogen, C1-C 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl groups; Each R c Each represents C1-C independently. 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl groups; E represents arbitrarily selected by one or more R. d Replacement C6-C 120 aryl, optionally with one or more R e The substituted 5-120 heteroaryl group or optionally replaced by one or more R f Replacement Wherein, * indicates a linking bond of a group; D1 represents B or N; D3 represents -C(=O)- or -S(=O)2- or is absent, and when D3 is absent, the carbon atom attached to it is hydrogen-terminated; D2 represents -N(Ar)-, -P(=O)(Ar)-, -C(=O)- or -S(=O)2-; D4 represents -O-, -S-, -Se-, -Te-, -N(Ar)-, -P(=O)(Ar)-, -C(=O)- or -S(=O)2-; each Ar independently represents an atom optionally bounded by one or more R groups. g Replacement C6-C 18 aryl or optionally substituted with one or more R g The substituted 5-18 heteroaryl groups, each Ar, may optionally exist independently or via a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R) h - is attached to an unsubstituted carbon atom on an adjacent aryl or heteroaryl group; Each R d Each independently represents a cyano group, optionally with one or more R groups. h Replacement C1-C 15 Alkyl, optionally with one or more R h Replacement C6-C 18 aryl or optionally substituted with one or more R h Replacement -N(R) x )2; Each R x Each represents C1-C independently. 15 Alkyl or C6-C 18 Aryl; Each R e R f R g Each independently represents a cyano group, optionally with one or more R groups. h Replacement C1-C 15 Alkyl, optionally with one or more R h Replacement C6-C 18 aryl, optionally with one or more R h The substituted 5-18 heteroaryl group or optionally replaced by one or more R h Replacement -N(R) y )2; Each R y Each represents C1-C independently. 15 Alkyl or C6-C 18 Aryl; Each R h Each represents C1-C independently. 15 Alkyl groups or optionally one or more C6-C 18 Aryl-substituted C6-C 18 Aryl; A represents any one or more R's. i Replacement Optional by one or more R i Replacement Or C6-C substituted with one or more cyano groups 18 Aryl; where * indicates a linking bond; D5, D6, and D7 each independently represent N or CH, and at least one is N; D8, D9, and D 10 Each represents C1-C independently. 15 Alkyl, C1-C 15 cycloalkyl, C6-C 18 Aryl or 5-18 heteroaryl groups, or none at all; D 11 D 12 Each can independently represent -O-, -S-, -S(=O)2-, -Se-, or -Te-, or may not exist; Each R i Each represents C1-C independently. 15 Alkyl, C1-C 15 Haloalkyl, C6-C 18 Aryl or 5-18 heteroaryl groups; K1 and K2 independently represent C1-C 15 Alkyl, optionally with one or more R j Replacement C6-C 18 aryl or optionally substituted with one or more R j The substituted 5-18 heteroaryl groups may not exist; Each R j Each represents C1-C independently. 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl compounds.

2. The compound according to claim 1, characterized in that, E represents arbitrarily selected by one or more R. f The following groups are substituted: Where Y1 represents a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R) h - or does not exist, R h It has the definition as described in claim 1; D4 has the definition as described in claim 1; n is selected from any integer from 0 to 3; * represents the linking bond of a group; R f It has the definition as described in claim 1; Preferably, E represents the option to be arbitrarily controlled by one or more Rs. f The following groups are substituted: Where Y1 and Y2 independently represent single bonds, -O-, -S-, -Se-, -Te-, -C(=O)-, -S(=O)2-, or -N(R)-. h - or does not exist, R h It has the definition described in claim 1; Y3 represents a single bond, -O-, -S-, -Se-, -Te-, -C(=O)-, or -S(=O)2-; * represents a linking bond of a group; R f It has the definition as described in claim 1; More preferably, E represents the option to be arbitrarily controlled by one or more Rs. f The following groups are substituted: Where * represents the linking bond of a group; R f It has the definition described in claim 1.

3. The compound according to claim 1, characterized in that, E represents arbitrarily selected by one or more R. f The following groups are substituted: Where Z1 and Z2 independently represent -N(Ar)-, -P(=O)(Ar)-, -C(=O)-, or -S(=O)2-; Z3 represents -N(Ar)-, -P(=O)(Ar)-, -C(=O)-, or -S(=O)2-, or is absent; * indicates the linking bond of the group; Ar, R f It has the definition as described in claim 1; Preferably, E represents the option to be arbitrarily controlled by one or more Rs. f The following groups are substituted: Where * represents the linking bond of a group; R f It has the definition described in claim 1.

4. The compound according to claim 1, characterized in that, E represents arbitrarily selected by one or more R. d The following groups are substituted: Where n is selected from any integer from 1 to 4, preferably 1 or 2; * represents the linking bond of the group; R d It has the definition described in claim 1.

5. The compound according to claim 1, characterized in that, E represents arbitrarily selected by one or more R. e The following groups are substituted: Where Ar1 and Ar2 each independently represent arbitrarily selected by one or more R e Replacement C6-C 18 aryl or optionally substituted with one or more R e The substituted 5-18 membered heteroaryl groups, Ar1 and Ar2, are each independently and optionally linked to an unsubstituted carbon atom on an adjacent aryl or heteroaryl group via a single bond; R e It has the definition as described in claim 1; * indicates a linking bond of a group; Preferably, E represents the option to be arbitrarily controlled by one or more Rs. e The following groups are substituted: Among them, R e It has the definition as described in claim 1; * indicates the linking bond of a group.

6. The compound according to any one of claims 1-5, characterized in that, A represents any one or more R's. i The following groups are substituted: Where * represents the linking bond of a group; R i It has the definition described in claim 1.

7. The compound according to any one of claims 1-6, characterized in that, X represents -C(R) a (R) b -, -O-, -S-, -Se-, -Te- or single bonds; R a R b Each independently represents hydrogen or C1-C. 15 alkyl.

8. The compound according to any one of claims 1-7, characterized in that, F1 and F2 each independently represent -C(R) a (R) b -, -O-, -S-, -Se-, -Te- or single bonds or none at all; when at least one of F1 and F2 is absent, the carbon atom attached to it is hydrogen-terminated; R a R b Each independently represents hydrogen or C1-C. 15 alkyl.

9. The compound according to any one of claims 1-8, characterized in that, R1 represents hydrogen, halogen atom, C1-C 15 Alkyl, C1-C 15 Haloalkyl, C1-C 15 Alkyl groups, -S(C1-C 15 alkyl), -Si(R) 16 (R) 17 (R) 18 ), can be arbitrarily controlled by one or more R c Replacement -N(R) 16 (R) 17 C6-C 18 Aryl or 5-18 heteroaryl; each R 16 R 17 R 18 Each independently represents hydrogen, C1-C 15 Alkyl, C6-C 18 Aryl or 5-18 heteroaryl; each R c Each represents C1-C independently. 15 alkyl; Preferably, R1 represents hydrogen, C1-C 15 Alkyl or optionally with one or more R c Replacement -N(R) 16 (R) 17 ); R 16 R 17 Each represents C6-C independently. 18 Aryl; each R c Each represents C1-C independently. 15 alkyl; R5, R8, R 11 Each independently represents hydrogen, C1-C 15 Alkyl or C6-C 18 Aryl; R2-R4, R6-R7, R9-R 10 R 12 -R 15 It represents hydrogen.

10. The following compounds:

11. An organic electroluminescent device, comprising, from bottom to top, a substrate, a first electrode, an organic functional material layer, and a second electrode, wherein, The organic functional material layer includes: The hole transport region is located above the first electrode; A light-emitting layer, located above the hole transport region, comprises a host material and a light-emitting material; The electron transport region is located above the light-emitting layer; The light-emitting layer comprises the compound according to any one of claims 1-10; Preferably, the luminescent material in the luminescent layer comprises a compound according to any one of claims 1-10; Preferably, the organic functional material layer further includes at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

12. A display device comprising the organic electroluminescent device according to claim 11.

13. A lighting device comprising the organic electroluminescent device according to claim 11.

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