Polar boron-nitrogen luminescent material, application thereof, and organic electroluminescent device containing the same

Abstract

The present invention relates to a polar boron-nitrogen luminescent material, and in particular to a resonance-type organic compound, its application, and an organic electroluminescent device containing the compound. The luminescent material has the following structure: wherein Y represents N or B, ring A, ring B, ring C, ring D, ring E, and ring F each independently represent a C6-C20 aromatic ring or a C5-C20 heteroaromatic ring, n1, n2, and n3 are each independently 0 or 1, and X 1 、X 2 and X 3 Each of the compounds is independently selected from a single bond, CR1R2, NR3, BR4, SiR5R6, O, S, C=O, or S(=O)2. The compounds of the present invention, with their B-N polar bonds doped into an MR resonant skeleton, exhibit significant advantages in optoelectronic properties when used as luminescent materials. When used as luminescent materials in OLED devices, they exhibit significant advantages in adjusting light color, increasing quantum yield, and improving device life. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a luminescent material, belonging to the technical field of organic electroluminescence, and in particular to a resonance-type organic compound and application thereof, and an organic electroluminescent device containing the compound. Background Art

[0002] With the continuous advancement of science and technology and the rapid development of information display, display technology is gradually moving from high-definition display to ultra-high-definition display (UHD), and is driving the digital transformation of industries centered on display. The new generation of ultra-high-definition video production and display system BT.2020 redefines the CIE color coordinates of the three primary colors of red (0.708, 0.292), green (0.170, 0.797), and blue (0.131, 0.046). Its color gamut space is much higher than the 35.9% of the traditional high-definition display BT.709. However, achieving a wide color gamut space requires narrow-spectrum luminescent materials with high color purity, which poses new challenges to the research of luminescent materials, especially three-primary color luminescent materials with a full width at half maxima (FWHM) of less than 30nm. Although organic light-emitting diode (OLED) technology has been commercialized, existing commercial luminescent materials (fluorescent and phosphorescent materials) typically have a wide Full Width Half Maximum (FWHM) (>40nm), requiring the use of optical filters or microcavity structures to adjust the spectrum. This significantly reduces the device's brightness and luminous efficiency, hindering the development of ultra-high-definition OLED display technology. Therefore, the design and development of narrow-spectrum luminescent material systems that can achieve high efficiency and high color purity under intrinsic conditions is a critical and challenging scientific issue for realizing OLED ultra-high-definition display technology.

[0003] In 2016, Hatakeyama's research group proposed a strategy for constructing a novel polycyclic rigid skeleton with multiple resonance (MR) effects to address the wide half-width of organic light-emitting materials. This strategy has attracted widespread attention from both the scientific research community and the industry. The most notable MR material is the blue organic light-emitting material v-DABNA, which was successfully developed by the research group in 2019 using the boron-nitrogen resonance effect. Its color purity exceeds that of gallium nitride and quantum dots. The half-width of its electroluminescent device is only 18nm, and the maximum external quantum efficiency reaches 34.4%. However, although the development of narrow-spectrum light-emitting materials based on this type of B,N resonant skeleton system has made great progress in recent years, and it has been proven that this type of material is an effective strategy for achieving high-efficiency, full-color narrow-spectrum organic light-emitting materials, there are still many problems that need to be solved, such as the single molecular design and difficult synthesis. On the one hand, the structural design of luminescent materials is relatively simple, resulting in the current lack of MR material systems capable of achieving narrow-spectrum emission across the full color range. Furthermore, the relationship between material structure design and FWHM requires further research. More importantly, the boronization reaction conditions for these MR materials are harsh, requiring multiple steps and resulting in low yields, making mass production difficult. This significantly limits the industrial development of narrow-spectrum OLED materials.

[0004] Compared to the aforementioned B- and N-doped polycyclic aromatic hydrocarbons (PAHs), the construction of BN-doped conjugated systems using isoelectronic boron-nitrogen (BN) bonds to replace carbon-carbon double bonds (C═C) in PAH backbones has a longer history, simpler synthesis methods, and has become an effective strategy for enriching and innovating organic functional materials. BN-covalently doped condensed aromatic compounds have skeletons similar to those of pure carbon aromatic hydrocarbon derivatives but exhibit unique optoelectronic properties. For example, the dipole effect of BN in regulating the molecular arrangement of the π-conjugated system and its excellent hole (electron) mobility have led to its widespread application in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). Furthermore, BN-doped condensed aromatic compounds have also been initially used in OLEDs, demonstrating the feasibility of this class of materials for electroluminescent devices. Therefore, developing ultra-high-definition display technologies based on BN-covalently doped luminescent materials offers unique advantages and strong appeal in meeting the BT.2020 display specifications. Summary of the Invention

[0005] To address the aforementioned issues in the prior art, the present applicants have provided a resonant organic compound and its application. The framework represented by general formula (1) is a BN covalently doped MR resonant backbone, which constructs a novel organic narrow-spectrum luminescent material. The polar BN doped MR resonant backbone exhibits significant advantages in optoelectronic properties, including the ability to significantly adjust light color, increase quantum yield, and improve device life.

[0006] The technical solution of the present invention is as follows: A luminescent material, the general structural formula of which is shown in general formula (1):

[0007]

[0008] In formula (1), the dotted line represents connection or non-connection;

[0009] Y stands for N or B;

[0010] Ring A, Ring B, Ring C, Ring D, Ring E, and Ring F each independently represent any one of a C6-C20 aromatic ring and a C5-C20 heteroaromatic ring;

[0011] n1, n2, and n3 are each independently 0 or 1;

[0012] X 1 、X 2 and X 3 are independently selected from a single bond, CR1R2, NR3, BR4, SiR5R6, O, S, C=O or S(=O)2;

[0013] Preferably, the X 1 、X 2 and X 3 are single bonds at the same time; or, when X 1 and X 3 When both are single keys, X 2 is CR1R2, NR3, BR4, SiR5R6, O, S; or, when X 1 and X 3 When it is CR1R2, NR3, BR4, SiR5R6, O, or S at the same time, X 2 For BR4;

[0014] R1, R2, R3, R4, R5, and R6 are independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 condensed ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl, or C5-C60 condensed ring heteroaryl;

[0015] R a 、R b 、R c 、R d 、R e 、R f and R g Each independently represents a substituent up to the maximum allowed number of substituents, and is independently selected from hydrogen, deuterium, halogen, or one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, and C5-C60 monoheteroaryl; R g is selected from one of C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, and C5-C60 heteroaryl; and said R a 、R b 、R c 、R d 、R e 、R f and R g Two adjacent ones of them may be connected by a single bond or may be fused to form a ring;

[0016] When the above R1, R2, R3, R4, R5, R6, a 、R b 、R c 、R d 、R e and R f When substituents are present, the substituents are independently selected from any one of deuterium, halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 condensed ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl, and C5-C60 condensed ring heteroaryl.

[0017] Preferably, the specific general formula of the compound of the present invention is the structure shown in any one of the following formulas (2), (3), (4), (5), (6) or (7):

[0018]

[0019] In formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7), X 1 、X2 、X 3 、n1、n2、n3、R a 、R b 、R c 、R d 、R e 、R f and R g The definitions of are the same as those in formula (1).

[0020] More preferably, in formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7), the X 2 is a single bond, n2 is 0 or 1; or, the X 1 、X 2 and X 3 are single bonds at the same time; or, when X 1 and X 3 When both are single keys, X 2 is CR1R2, NR3, BR4, SiR5R6, O, S; or, when X 1 and X 3 When X is one of CR1R2, NR3, BR4, SiR5R6, O, or S, 2 It is BR4.

[0021] Preferably, the specific general formula of the compound of the present invention is the structure shown in the following formula (8) or formula (9):

[0022]

[0023] In formula (8) and formula (9), the dotted line represents connection or non-connection; X 1 、X 2 、X 3 、n1、n2、n3、R a 、R c 、R d 、R e 、R f and R g The definitions of are the same as those in formula (1);

[0024] Preferably, in formula (8) and formula (9), the dotted line represents a connection;

[0025] Preferably, in formula (8) and formula (9), the X 2 is a single bond, n2 is 0 or 1; or, the X 1 、X 2 and X 3 are single bonds at the same time; or, when X 1 and X 3 When both are single keys, X 2is CR1R2, NR3, BR4, SiR5R6, O, S; or, when X 1 and X 3 When X is one of CR1R2, NR3, BR4, SiR5R6, O, or S, 2 It is BR4.

[0026] Further preferably, in formula (1) to formula (9), the ring A, ring B, ring C, ring D, ring E, and ring F each independently represent any one of a C6-C10 aromatic ring or a C5-C10 heteroaromatic ring; more preferably, the ring A, ring B, ring C, ring D, ring E, and ring F each independently represent a benzene ring or a naphthalene ring; or preferably, the ring A, ring B, ring C, ring D, ring E, and ring F each independently represent a benzene ring, a naphthalene ring, or a pyridine ring.

[0027] Preferably, in formula (1) to formula (9), R a 、R b 、R c 、R d 、R e 、R f and R g Each is independently selected from one of hydrogen, deuterium, halogen, C1-C6 chain alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 thioalkoxy, cyano, C6-C20 arylamino, C3-C20 heteroarylamino, C6-C30 aryl, C6-C30 aryloxy, and C5-C30 heteroaryl; the R a 、R b 、R c 、R d 、R e 、R f and R g Two adjacent ones of them may be connected by a single bond or may be fused to form a ring;

[0028] Further, R a 、R b 、R c 、R d 、R e 、R fare independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, tetraphenylenyl, pentacene, benzopyrenyl, biphenyl, aphenylene, terphenyl, triphenylene, tetraphenylenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1 , 2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, pyrrole, piperidine, methoxy, silicon, or a combination of two of the above substituent groups;

[0029] More preferably, the R a 、R b 、R c 、R d 、R e 、R fare independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methylbutyl, trifluoromethyl, pentafluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, tetraphenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenylene, tetraphenylene, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, phenyl thiophene, isobenzothiophene, dibenzothiophene, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl , phenanthrozolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl oxazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy or silicon.

[0030] Further preferably, in formula (1) to formula (9), the R gselected from phenyl, naphthyl, anthracenyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, neohexyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, fluoranthenyl, tetraphenylenyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, triphenylene, tetraphenylenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis- indenofluorenyl, trimeric indenyl, isotrimeric indenyl, spirotrimeric indenyl, spiroisotrimeric indenyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthioimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthioxazolyl, anthracene oxazolyl, phenanthrozolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5- One of oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, and silicon.

[0031] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents (at least 2), they may be the same or different substituents. When the same expression is mentioned below, it has the same meaning, and the selection range of the substituents is as shown above and will not be repeated one by one.

[0032] In the present invention, the halogen may be fluorine, chlorine, bromine or iodine. The following descriptions of the same elements have the same meanings.

[0033] In the present invention, unless otherwise specified, the expression of chemical elements includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1H (protium), 2H (deuterium, D), 3H (tritium, T), etc.; carbon (C) includes 12C, 13C, etc.

[0034] In the present invention, unless otherwise specified, the heteroatom of the heteroaryl group is selected from N, O, S, P, B, Si or Se.

[0035] In the present invention, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0036] In the present invention, the expression of Ca to Cb means that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms in the substituent.

[0037] In the present invention, “each independently” means that when there are multiple subjects, they may be the same or different.

[0038] In the present invention, the C6 to C60 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.

[0039] The C3~C60 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.

[0040] The C1 to C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0041] The C3 to C20 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.

[0042] The C1 to C36 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C25, C28, C30, C32, C34 or C35, etc.

[0043] The C3 to C20 can all be C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C20, etc.

[0044] The C1 to C10 can all be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0045] The C6 to C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0046] The C3 to C30 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0047] In the present invention, the C6-C60 aromatic ring, preferably a C6-C30 aromatic ring, further preferably a C6-C20 aromatic ring, includes a single aromatic ring and a condensed aromatic ring; the single aromatic ring includes a benzene ring, and the condensed aromatic ring means that the ring contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms to condense with each other, illustratively including but not limited to: naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring and its derivatives (9,9-dimethylfluorene ring, 9,9-diphenylfluorene ring, 9,9-dinaphthylfluorene ring, spirobifluorene ring, benzofluorene ring, etc.), fluoranthene ring, triphenylene ring, pyrene ring, perylene ring, Ring or tetracene ring, etc.

[0048] The C3-C60 heteroaromatic ring, preferably a C3-C30 heteroaromatic ring, more preferably a C3-C20 heteroaromatic ring, includes a single heteroaromatic ring or a condensed heteroaromatic ring. The single heteroaromatic ring illustratively includes, but is not limited to, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a furan ring, a thiophene ring, a pyrrole ring, and the like. The fused heteroaromatic ring means that the ring structure contains at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), and the two share two adjacent atoms to be fused with each other, and exemplarily includes but is not limited to: quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, isobenzothiophene ring, indole ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring and its derivatives (N-phenylcarbazole ring, N-naphthylcarbazole ring, benzocarbazole ring, dibenzocarbazole ring, indolecarbazole ring, azacarbazole ring, etc.), acridine ring, phenothiazine ring, phenoxazine ring, hydroacridine ring, etc.

[0049] The C6-C60 aryl group, preferably a C6-C30 aryl group, further preferably a C6-C20 aryl group, includes a monocyclic aryl group and a condensed ring aryl group; the monocyclic aryl group means that the group contains at least one phenyl group, and when it contains at least two phenyl groups, the phenyl groups are connected by a single bond, and illustratively include but are not limited to: phenyl, biphenyl, terphenyl, etc.; the condensed ring aryl group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms and are fused to each other, and illustratively include but are not limited to: naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives (9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirobifluorenyl, benzofluorenyl, etc.), fluoranthenyl, triphenylene, pyrenyl, perylene, phenyl or tetraphenyl etc.

[0050] The C3-C60 heteroaryl group, preferably a C3-C30 heteroaryl group, more preferably a C3-C20 heteroaryl group, includes a monocyclic heteroaryl group or a condensed-ring heteroaryl group. The monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains a heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other group are connected by a single bond. Exemplary examples include but are not limited to: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, etc. The fused-ring heteroaryl group refers to a group containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring) in the molecule, and the two share two adjacent atoms fused to each other, including but not limited to: quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl and its derivatives (N-phenylcarbazolyl, N-naphthylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolecarbazolyl, azacarbazolyl, etc.), acridinyl, phenothiazinyl, phenoxazinyl, hydroacridinyl, etc.

[0051] The C1-C36 chain alkyl group specifically includes a straight chain or branched chain alkyl group, preferably a C1-C20 straight chain or branched chain alkyl group, further preferably a C1-C16 straight chain or branched chain alkyl group, and further preferably a C1-C10 straight chain or branched chain alkyl group, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0052] The C3-C20 cycloalkyl group, preferably a C3-C10 cycloalkyl group, illustratively includes but is not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and the like.

[0053] The C3-C20 heterocycloalkyl group is further preferably a C3-C10 heterocycloalkyl group, i.e., a group formed by replacing at least one carbon atom in the cycloalkyl group listed above with a heteroatom (such as O, S or N, etc.), illustratively including but not limited to: tetrahydropyrrolyl, tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, dioxaneyl, etc.

[0054] In the present invention, the aryloxy group is a monovalent group consisting of the above-mentioned aryl group and oxygen, and the heteroaryloxy group is a monovalent group consisting of the above-mentioned heteroaryl group and oxygen.

[0055] Furthermore, the compounds of the general formula (1) of the present invention can preferably include the following specific structures, Compounds 1 to 322, which are only representative:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by any one of the above-mentioned general formulas (1) to (9), or the organic layer comprises any one of the above-mentioned compounds 1 to 322.

[0067] Specifically, an embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a light-emitting layer is formed between the hole transport layer and the electron transport layer; wherein, preferably, the light-emitting layer contains a compound of the general formula of the present invention represented by any one of the above-mentioned general formulas (1) to (9).

[0068] The general compound of the present invention (see the formula below) utilizes a BN covalently doped MR resonant backbone to construct a novel organic narrow-spectrum luminescent material. The BN embedding maintains the planar structure of the MR backbone while imparting unique photophysical properties, such as bipolar carrier transport and intermolecular dipole-dipole interactions. This type of material offers advantages in synthesis, with a three-step synthesis method yielding the target material. The borylation reaction is simple and yields high yields exceeding 90%. Compared with traditional borylation reactions, the compounds of the present invention are more amenable to large-scale production. Furthermore, by optimizing the material structure through the use of a parent core, peripheral substituents, and fused ring parallel connection, the material exhibits a fluorescence spectrum with a full width at half maximum (FWHM) of only 26-32 nm and a PLQY >90%, demonstrating high brightness.

[0069]

[0070] Specifically, ring A, ring B, ring C, ring D, ring E, and ring F in the general formula of the present invention can be independently selected from one of a benzene ring, a naphthalene ring, and an aza-fused ring. Although these groups have different electron-donating or electron-withdrawing abilities, when introduced into the general formula of the compound of the present invention, they significantly adjust the photophysical properties of the compound of the present invention, such as red-shift and blue-shift of absorption and emission. Since the molecular structure of the compound of the present invention has a rigid π-conjugated plane, the luminescence of the molecule mainly comes from short-range intramolecular charge transfer. Therefore, the ring AF has little effect on the half-value width and photoluminescence quantum efficiency of the compound of the present invention, and can obtain ideal photophysical properties. In combination with a more preferred embodiment, such as the X 1 、X 2 and X 3 When they are single bonds at the same time; when the peripheral groups are all carbazole groups, due to the relatively weak electron-donating ability of the carbazole group, the excited state electrons of this series of compounds are delocalized on the entire conjugated plane, and the luminescence performance and stability of the material are greatly improved. For example, in another parallel scheme, when X 1 and X 3 When it is CR1R2, NR3, BR4, SiR5R6, O, or S at the same time, X 2 BR4. In particular, X 2 When Y is BR4, the central skeleton of the compound of the present invention constitutes a triangular planar configuration surrounded by three boron atoms. The empty p orbital of the boron center can be effectively conjugated with adjacent heterocyclic rings such as benzene rings, greatly improving the photoelectric properties of the material. When Y is a nitrogen atom, it can form an effective multiple resonance effect with the nitrogen atom, thereby effectively narrowing the half-peak width of the luminescent material.

[0071] In the general formula of the present invention, Y is selected from N or B. As mentioned above, when Y is a nitrogen atom, the half-peak width of the luminescent material can be effectively narrowed; when Y is a boron atom, the central skeleton of the compound of the present invention contains three boron atoms, which can enhance the electron-deficient characteristics of the central skeleton. 1 and X 3When one of CR1R2, NR3, SiR5R6, O, or S is present at the same time, a short-range intramolecular charge transfer process can be formed within the molecule, and the material exhibits low polarity. Combined with the rigid molecular planar structure, the compound of the present invention can also maintain a relatively narrow luminescence half-width. At the same time, the energy difference between its lowest energy excited singlet state and excited triplet state is reduced, which is conducive to the reverse intersystem crossing of the lowest triplet state exciton and enhances the thermally activated delayed fluorescence characteristics. In summary, the compound of the present invention combines the unique photophysical properties of the boron-nitrogen polar bond and the boron-nitrogen structure with a multiple resonance effect, realizing a simple, efficient, and large-scale production method. This provides a direction for the development and commercialization of multiple resonance narrow spectrum materials, and greatly enriches the skeleton system of multiple resonance narrow spectrum materials. There is great hope for screening to obtain high color purity and high efficiency three-primary color narrow spectrum organic light-emitting materials.

[0072] The electroluminescence spectrum of the OLED device prepared using the compound of the present invention has a narrow half-width at half maximum and shows a significant multiple resonance effect, thereby greatly enriching the material system of multiple resonance-thermally activated delayed fluorescence, while greatly optimizing the synthesis process and improving the reaction yield; in terms of OLED devices, they have a low starting voltage, high luminous efficiency and a better service life, which can meet the current requirements of panel manufacturers for high-performance materials and show good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 : The electroluminescence spectrum of the organic electroluminescent device D1 prepared in this embodiment of the present invention is shown in the figure.

[0074] Figure 2 : Schematic diagram of the structure of the organic electroluminescent device prepared by the present invention, in which 1 is a substrate, 2 is an anode, 3 is a hole transport layer, 4 is an organic light-emitting layer, 5 is an electron transport layer, and 6 is a cathode. DETAILED DESCRIPTION

[0075] The specific preparation method of the above-mentioned novel compound of the present invention will be described in detail below using a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.

[0076] Various chemicals used in the present invention, such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N,N-diisopropylethylamine, reaction intermediates, and other basic chemical raw materials, were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd. The mass spectrometer used to determine the following compounds was a ZAB-HS mass spectrometer (manufactured by Micromass, UK).

[0077] The synthesis method of the compound of the present invention is briefly described below. First, a nucleophilic substitution reaction is used to obtain an intermediate compound (1). Then, a boron ester is added and a Suzuki coupling reaction is performed to obtain an intermediate (2). Finally, an amino-directed electrophilic borylation reaction is performed to obtain the target compound.

[0078] Example 1 Synthesis of Compound 4:

[0079]

[0080] Preparation of intermediate B1:

[0081] To a three-necked flask, raw material A1 (10 mmol) and 50 mL of anhydrous DMF were added in sequence, and under nitrogen protection, Cs2CO3 (40 mmol) and carbazole (20 mmol) were added, and the mixture was heated and stirred for 24 hours. After the reaction was completed, 100 mL of water was added to quench the reaction, and a large amount of white precipitate was filtered. The precipitate was collected and dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain intermediate B1. LC-MS: Measured value: 566.97 ([M+H] + ), theoretical value: 565.98.

[0082] Preparation of intermediate C1:

[0083] In a two-necked flask, under a nitrogen atmosphere, the intermediate B1 compound (3.6 mmol) was dissolved in 30 mL of a mixture of dimethyl ether and water (3:1). Diphenylamine borate (8.7 mmol), potassium carbonate (36.2 mmol), and tetrakis(triphenylphosphine)palladium (0.36 mmol) were added, and the temperature was then raised to 80°C for 16 hours. The solvent was dried under vacuum and passed through a silica gel column (developing solvent: petroleum ether: CH2Cl2 = 10:1) to obtain the target intermediate C1 (2.8 g, 81% yield, HPLC analysis purity 99.65%) as a yellow solid. LC-MS: Measured value: 948.48 ([M+H] + ), theoretical value: 947.51

[0084] Preparation of compound 4:

[0085] Intermediate C1 (0.8 mmol) was dissolved in 30 ml of chlorobenzene, and boron tribromide (3.3 mmol) and triethylamine (8.1 mmol) were added. The temperature was raised to 150°C and the reaction was allowed to react for 18 hours. The solvent was evaporated in vacuo, and the product was passed through a silica gel column (developing solvent: petroleum ether:CH2Cl2 = 10:1) to obtain the target compound 4 (91% yield, 99.22% purity by HPLC) as a yellow solid. 1H NMR (600 MHz, Methylene Chloride-d2)δ(ppm):8.95(d,J=7.4Hz,2H),8.52(d,J=8.5Hz,2H),8.35(d,J=8. 4Hz,2H),8.19(d,J=7.3Hz,2H),8.08(d,J=2.1Hz,2H),8.02(d,J=1.7Hz,2H),7.5 5(t,J=7.4Hz,2H),7.49(dd,J=8.5,2.0Hz,2H),7.31(d,J=7.4Hz,2H),7.24–7.18 (m,2H),7.12(d,J=8.2Hz,2H),6.64(d,J=1.7Hz,2H),1.47(s,18H),0.73(s,18H). 13 C NMR(151MHz,Methylene Chloride-d2)δ(ppm):145.56,141.44,139.57,132.41,126.49,126.48,126.19, 124.98,124.96,124.65,124.63,123.88,122.98,122.40,121.05,120.50,117.87 ,116.85,115.70,53.81,53.64,53.46,53.27,53.09,34.89,34.88,34.54,34.53, 31.62,31.61,30.89,30.88.MALDI-TOF:Calculated:978.0432,Found:978.1663.

[0086] Example 2 Synthesis of Compound 129:

[0087]

[0088] Preparation of intermediate B2:

[0089] To a three-necked flask, raw material A1 (10 mmol) and 50 mL of anhydrous DMF were added in sequence, and under nitrogen protection, Cs2CO3 (40 mmol) and 3,6-di-tert-butylcarbazole (20 mmol) were added, and the mixture was heated and stirred for 24 hours. After the reaction was completed, 100 mL of water was added to quench the reaction, and a large amount of white precipitate was filtered. The precipitate was collected and dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain intermediate B2. LC-MS: Measured value: 791.63 ([M+H] + ), theoretical value: 790.73.

[0090] Preparation of intermediate C2:

[0091] In a two-necked flask, under a nitrogen atmosphere, the intermediate B2 compound (3.6 mmol) was dissolved in 30 mL of a mixture of dimethyl ether and water (3:1). Diphenylamine borate (8.7 mmol), potassium carbonate (36.2 mmol), and tetrakis(triphenylphosphine)palladium (0.36 mmol) were added, and the temperature was then raised to 80°C to react for 16 hours. The solvent was dried under vacuum and passed through a silica gel column (developing solvent: petroleum ether: CH2Cl2 = 10:1) to obtain the target intermediate C1 (2.8 g, 81% yield, HPLC analysis purity 99.65%) as a yellow solid. LC-MS: Measured value: 948.48 ([M+H] + ), theoretical value: 947.51

[0092] Preparation of compound 129:

[0093] Intermediate C2 (0.8 mmol) was dissolved in 30 ml of chlorobenzene, and boron tribromide (3.3 mmol) and triethylamine (8.1 mmol) were added. The temperature was raised to 150°C and the reaction was allowed to react for 18 hours. The solvent was evaporated in vacuo, and the product was passed through a silica gel column (developing solvent: petroleum ether:CH2Cl2 = 10:1) to obtain the target compound 4 (91% yield, 99.22% purity by HPLC) as a yellow solid. 1 H NMR (400 MHz, Methylene Chloride-d2)δ(ppm):9.18(d,J=1.5Hz,2H),8.87(d,J=8.2Hz,2H),8.72(d,J=1.7 Hz,2H),8.41(d,J=1.8Hz,2H),8.14(dd,J=7.5,1.1Hz,2H),7.98(d,J=7.1Hz,2H),7 .63(t,J=7.2Hz,2H),7.49(t,J=7.4Hz,2H),7.22(dd,J=8.7,1.8Hz,2H),6.88(d,J =8.4Hz,2H),6.78–6.70(m,2H),6.38(d,J=8.3Hz,2H),1.65(s,18H),1.43(s,18H). 13C NMR(101MHz,Methylene Chloride-d2)δ(ppm):145.76,143.33,143.20,142.93,142.02,141.88,137.62, 129.83,129.04,126.39,126.21,125.80,124.82,123.51,122.64,122.33,120.9 1,120.81,120.63,116.84,116.44,109.74,54.01,53.74,53.47,53.20,52.93,3 5.69,34.74,32.08,31.79.MALDI-TOF:Calculated:978.5004,Found:978.1663.

[0094] Example 3 Synthesis of Compound 110:

[0095]

[0096] Synthesis of intermediate B3:

[0097] The synthesis of intermediate B3 was similar to that of intermediate B1, except that diphenylamine was used instead of carbazole to obtain intermediate B3. LC-MS: Measured value: 480.21 ([M+H] + ), theoretical value: 479.21.

[0098] Synthesis of intermediate C3:

[0099] The synthesis of intermediate C3 was based on intermediate C2, except that intermediate B3 was used instead of intermediate B2 to obtain intermediate C3. LC-MS: Measured value: 652.83 ([M+H] + ), theoretical value: 651.81.

[0100] Synthesis of intermediate C3a:

[0101] The synthesis of intermediate C3a was based on the synthesis of compound 129, except that intermediate C3 was used instead of intermediate C2 to obtain intermediate C3a. LC-MS: Measured value: 668.30 ([M+H] + ), theoretical value: 663.35.

[0102] Synthesis of compound 110:

[0103] Intermediate C3a was dissolved in 30 ml of dichloromethane, and trifluoromethanesulfonic acid and dichlorodicyanobenzoquinone were added. After 1 hour of reaction, 100 ml of water was added to quench the reaction, and the large amount of white precipitate was filtered. The precipitate was collected and dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified by silica gel column using petroleum ether:ethyl acetate = 500:1 as a developing solvent to obtain compound 110. LC-MS: Measured value: 668.24 ([M+H] + ), theoretical value: 667.38.

[0104] Example 4 Synthesis of Compound 113:

[0105]

[0106] Synthesis of intermediate B4:

[0107] The synthesis of intermediate B4 was similar to that of intermediate B1, except that phenoloxazine was used instead of carbazole to obtain intermediate B4. LC-MS: Measured value: 494.29 ([M+H] + ), theoretical value: 493.21.

[0108] Synthesis of intermediate C4:

[0109] The synthesis of intermediate C4 was based on intermediate C2, except that intermediate B4 was used instead of intermediate B2 to obtain intermediate C4. LC-MS: Measured value: 666.86 ([M+H] + ), theoretical value: 665.79.

[0110] Synthesis of compound 113:

[0111] The synthesis of compound 113 was carried out by referring to the synthesis of compound 129, except that intermediate C4 was used instead of intermediate C2 to obtain compound 113. LC-MS: Measured value: 682.39 ([M+H] + ), theoretical value: 681.37.

[0112] Example 5 Synthesis of Compound 195:

[0113]

[0114] Synthesis of intermediate B5:

[0115] To a two-necked flask were added raw material A3 (10.0 mmol), raw material A4 (10.0 mmol), Pd(PPh3)4 catalyst (0.1 mmol), 50 mL of a 10:1 tetrahydrofuran:water mixture, and potassium carbonate (20 mmol), followed by stirring at 80°C for 7.5 hours under nitrogen protection. After cooling, the liquids were separated and the organic phase was collected, dried over anhydrous sodium sulfate, filtered, and concentrated. The compound was separated by silica gel column using petroleum ether:ethyl acetate = 5:1 as the developing solvent to obtain intermediate B5. LC-MS: Measured value: 363.15 ([M+H] + ), theoretical value: 362.11.

[0116] Synthesis of intermediate B6:

[0117] To a two-necked flask, intermediate B5 (10.0 mmol) and triethylphosphine oxide (20.0 mmol) were added sequentially, followed by nitrogen protection, stirring and reflux for 24 hours. After cooling, the reaction solution was concentrated and separated by silica gel column using petroleum ether:ethyl acetate = 100:1 as the developing solvent to obtain intermediate B16. LC-MS: Measured value: 331.18 ([M+H] + ), theoretical value: 330.12.

[0118] Preparation of intermediate B7:

[0119] The synthesis of intermediate B16 was based on intermediate B2, except that intermediate B6 was used to replace 3,6-di-tert-butylcarbazole to obtain intermediate B7. LC-MS: Measured value: 641.35 ([M+H] + ), theoretical value: 640.38.

[0120] Preparation of intermediate C5:

[0121] The synthesis of intermediate C5 was based on intermediate C2, except that intermediate B7 was used instead of B2 to obtain intermediate C5. LC-MS: Measured value: 1038.26 ([M+H] + ), theoretical value: 1047.31.

[0122] Preparation of compound 195:

[0123] The synthesis of this example is basically the same as that of compound 129, except that the reactants shown in the figure are replaced in this example. The target compound 195 (0.6 g, 86% yield, HPLC analysis purity 99.56%) is a yellow solid. LC-MS: Measured value: 1053.88 ([M+H] + ), theoretical value: 1052.98.

[0124] Example 6 Synthesis of Compound 272:

[0125]

[0126] Preparation of intermediate B8:

[0127] To a two-necked flask, raw material A11 (10.0 mmol), 40 mL of anhydrous DMF, and NaH (11.0 mmol) were added in sequence and stirred at room temperature for 1 hour. Raw material A12 (10 mmol) dissolved in 10 mL of anhydrous DMF was then added and stirred at room temperature for 6 hours. 100 mL of water was added to precipitate a large amount of white solid. The solid was filtered and the precipitate was dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered. The organic phase was concentrated and the compound was separated by silica gel column using petroleum ether:ethyl acetate = 50:1 as the developing solvent to obtain intermediate B18. LC-MS: Measured value: 489.03 ([M+H] + ), theoretical value: 487.95.

[0128] Preparation of intermediate B9:

[0129] To a two-necked flask, intermediate B18 (5.0 mmol), 50 mL of N,N-dimethylformamide (DMAc), palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol), and triphenylphosphine (5 mmol) were added in sequence. The mixture was heated under reflux and stirred for 22 hours. The reaction solution was filtered and concentrated, and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B19. LC-MS: Measured value: 409.12 ([M+H] + ), theoretical value: 408.03.

[0130] Preparation of intermediate B10:

[0131] In a three-necked flask, under nitrogen protection, intermediate B9 (10 mmol), pinacol diboronate (20 mmol), potassium acetate (30 mmol), S-phos (2 mmol), and Pd2(dba)3 (0.4 mmol) were added to 250 mL of dioxane and refluxed for 7 h. The reaction system was cooled to room temperature, and the reaction mixture was diluted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure. The product was purified by silica gel column chromatography using n-heptane / ethyl acetate (9:1) as the eluent to obtain intermediate B10. LC-MS: Measured value: 330.33 ([M+H] + ), theoretical mass: 329.38.

[0132] Preparation of intermediate B11:

[0133] The synthesis of intermediate B11 was based on intermediate C2, except that intermediate B10 was used instead of intermediate B2 to obtain intermediate B11. LC-MS: Measured value: 776.76 ([M+H] + ), theoretical value: 776.82.

[0134] Preparation of intermediate C6:

[0135] The synthesis of intermediate C6 was based on intermediate C2, except that intermediate B11 was used instead of intermediate B2 to obtain intermediate C6. LC-MS: Measured value: 864.05 ([M+H] + ), theoretical value: 863.12.

[0136] Preparation of compound 272:

[0137] Compound 272 was prepared by referring to compound 129, except that intermediate C6 was used instead of intermediate C2 to obtain compound 272. LC-MS: Measured value: 879.55 ([M+H] + ), theoretical value: 878.69.

[0138] Example 7 Synthesis of Compound 281:

[0139]

[0140] Preparation of intermediate B12:

[0141] To a two-necked flask, raw material A8 (5.0 mmol), 50 mL of N,N-dimethylformamide (DMAc), palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol), and triphenylphosphine (5 mmol) were added in sequence. The mixture was heated under reflux and stirred for 25 hours. The reaction solution was filtered and concentrated, and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B12. LC-MS: Measured value: 242.11 ([M+H] + ), theoretical value: 241.09.

[0142] Preparation of intermediate B13:

[0143] To a two-necked flask, intermediate B12 (10.0 mmol), NBS (20.0 mmol), and 7 mL of anhydrous DMF were added in sequence. The mixture was then refluxed and stirred at 0°C for 12 hours under nitrogen protection. After cooling, the mixture was washed with anhydrous sodium sulfite solution (3×50 mL). The liquids were separated, and the organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was filtered and concentrated, and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B13. LC-MS: Measured value: 320.10 ([M+H] +), theoretical value: 319.00.

[0144] Preparation of intermediate B14:

[0145] To a two-necked flask were added intermediate B13 (10.0 mmol), starting material A9 (10.0 mmol), 0.1 mmol of Pd2(dba)3 catalyst, 20 mmol of potassium tert-butoxide, 0.3 mmol of tri-tert-butylphosphine, and 50 mL of toluene. The mixture was then stirred under reflux at 110°C for 4.5 hours under nitrogen atmosphere. After cooling, the organic phase was filtered and concentrated. The compound was separated by silica gel column chromatography using petroleum ether:ethyl acetate = 10:1 as the developing solvent to obtain intermediate B14 in a yield of 62.19%. LC-MS: Measured value: 401.10 ([M+H] + ), theoretical value: 400.05.

[0146] Preparation of intermediate B15:

[0147] To a two-necked flask, intermediate B14 (5.0 mmol), 50 mL of N,N-dimethylformamide (DMAc), palladium acetate (0.5 mmol), potassium carbonate (25.0 mmol), tetra-n-butylammonium bromide (2.5 mmol), and triphenylphosphine (5 mmol) were added in sequence. The mixture was heated under reflux and stirred for 20 hours. The reaction solution was filtered and concentrated, and the compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate B15. LC-MS: Measured value: 365.18 ([M+H] + ), theoretical value: 364.08.

[0148] Preparation of intermediate B16:

[0149] The synthesis of intermediate B16 was based on intermediate B10, except that intermediate B15 was used instead of intermediate B9 to obtain intermediate B16. LC-MS: Measured value: 330.32 ([M+H] + ), theoretical value: 329.38.

[0150] Preparation of intermediate C7:

[0151] The synthesis of intermediate C7 was based on intermediate C2, except that intermediate B17 was used instead of intermediate B2 to obtain intermediate C7. LC-MS: Measured value: 864.05 ([M+H] + ), theoretical value: 863.12.

[0152] Preparation of compound 281:

[0153] Compound 281 was prepared by referring to compound 129, except that intermediate C7 was used instead of intermediate C2 to obtain compound 281. LC-MS: Measured value: 879.55 ([M+H] + ), theoretical value: 878.69.

[0154] Example 8 Synthesis of Compound 231:

[0155]

[0156] Preparation of intermediate B18:

[0157] To a three-necked flask, raw material A10 (10 mmol) and 50 mL of anhydrous DMF were added in sequence, and under nitrogen protection, Cs2CO3 (20 mmol) and A11 (10 mmol) were added, and the mixture was heated and stirred for 24 hours. After the reaction was completed, 100 mL of water was added to quench the reaction, and a large amount of white precipitate was filtered. The precipitate was collected and dissolved in dichloromethane, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain intermediate B18. LC-MS: Measured value: 608.21 ([M+H] + ), theoretical value: 607.19.

[0158] Preparation of intermediate C8:

[0159] The synthesis of intermediate C8 was based on intermediate C2, except that intermediate B18 was used instead of intermediate B2 to obtain intermediate C8. LC-MS: Measured value: 780.82 ([M+H] + ), theoretical value: 779.79.

[0160] Preparation of compound 231:

[0161] Compound 231 was prepared by referring to compound 129, except that intermediate C8 was used instead of intermediate C2 to obtain compound 23

[0162] 1. LC-MS: Measured value: 796.42 ([M+H] + ), theoretical value: 795.37.

[0163] Example 9 Synthesis of Compound 234:

[0164]

[0165] Preparation of intermediate B19:

[0166] The synthesis of intermediate B19 was based on intermediate B18, except that raw material A13 was used instead of raw material A11 to obtain intermediate B19. LC-MS: Measured value: 567.31 ([M+H] + ), theoretical value: 566.29.

[0167] Preparation of intermediate C9:

[0168] The synthesis of intermediate C9 was based on intermediate C2, except that intermediate B19 was used instead of intermediate B2 to obtain intermediate C9. LC-MS: Measured value: 739.92 ([M+H] + ), theoretical value: 738.89.

[0169] Preparation of compound 234:

[0170] Compound 234 was prepared by referring to compound 129, except that intermediate C9 was used instead of intermediate C2 to obtain compound 234. LC-MS: Measured value: 755.41 ([M+H] + ), theoretical value: 754.46.

[0171] Example 10 Synthesis of Compound 300:

[0172]

[0173] Preparation of intermediate C11:

[0174] The synthesis of intermediate C10 refers to intermediate C2, except that raw material A15 is used instead of raw material A7 to obtain intermediate C11. LC-MS: Measured value: 1194.45 ([M+H] + ), theoretical value: 1193.59.

[0175] Preparation of compound 300:

[0176] Compound 300 was prepared by referring to compound 129, except that intermediate C11 was used instead of intermediate C2 to obtain compound 300. LC-MS: Measured value: 1210.26 ([M+H] + ), theoretical value: 1209.17.

[0177] Example 11 Synthesis of Compound 308:

[0178]

[0179] Preparation of intermediate C10:

[0180] The synthesis of intermediate C10 refers to intermediate C2, except that raw material A16 is used instead of raw material A7 to obtain intermediate C10. LC-MS: Measured value: 1044.26 ([M+H] + ), theoretical value: 1043.36.

[0181] Preparation of compound 308:

[0182] Compound 308 was prepared by referring to compound 129, except that intermediate C10 was used instead of intermediate C2 to obtain compound 308. LC-MS: Measured value: 1059.87 ([M+H] + ), theoretical value: 1058.94.

[0183] Example 12 Synthesis of Compound 179:

[0184]

[0185] Preparation of compound 179:

[0186] Compound 4 was dissolved in 30 ml of dichloromethane, trifluoromethanesulfonic acid and dichlorodicyanobenzoquinone were added, and after 1 hour of reaction, 100 ml of water was added to quench the reaction, and the large amount of white precipitate was filtered. The precipitate was collected and extracted with dichloromethane solution, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain compound 179. LC-MS: Measured value: 975.77 ([M+H] + ), theoretical value: 974.86.

[0187] Example 13 Synthesis of Compound 2:

[0188]

[0189] Preparation of intermediate B20:

[0190] Add raw material A17 (2 mmol) to a dry three-necked flask, add 20 mL of dry ether, then slowly add boron tribromide (2 mmol) dropwise at -10°C. After slowly returning to room temperature, react for 18 hours. Drain the solvent to obtain intermediate B20. LC-MS: Measured value: 243.91 ([M+H] + ), theoretical value: 242.91.

[0191] Preparation of intermediate B21:

[0192] The synthesis of intermediate B21 was based on intermediate B2, except that carbazole was used instead of 3,6-di-tert-butylcarbazole to obtain intermediate B21. LC-MS: Measured value: 527.89 ([M+H] +), theoretical value: 526.99.

[0193] Preparation of intermediate B22:

[0194] Intermediate B21 (5 mmol) was added to a dry three-necked flask, 30 mL of ether was added, and the mixture was cooled to -78°C. N-butyl lithium (5 mmol) was slowly added dropwise, and the mixture was reacted at -78°C for 1 hour. Intermediate 20 (6 mmol) was added to the reaction mixture, and the temperature was slowly raised to room temperature and the reaction was continued for 24 hours. After the reaction was completed, two drops of methanol were added, and the mixture was extracted with dichloromethane solution. After drying over anhydrous sodium sulfate and filtering, the reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain compound intermediate 22. LC-MS: Measured value: 564.10 ([M+H] + ), theoretical value: 563.09.

[0195] Preparation of intermediate C12:

[0196] The synthesis of intermediate C12 was based on intermediate C2, except that intermediate B22 was used instead of intermediate B2 to obtain intermediate C12. LC-MS: Measured value: 736.56 ([M+H] + ), theoretical value: 735.69.

[0197] Preparation of compound 2:

[0198] Compound 2 was prepared by referring to compound 129, except that intermediate C12 was used instead of intermediate C2 to obtain compound 2. LC-MS: Measured value: 752.34 ([M+H] + ), theoretical value: 751.27.

[0199] Example 14 Synthesis of Compound 74:

[0200]

[0201] Preparation of intermediate B23:

[0202] Add raw material A18 (2 mmol) to a dry three-necked flask, add 20 mL of dry ether, then slowly add boron tribromide (2 mmol) dropwise at -10°C. After slowly returning to room temperature, react for 18 hours. Drain the solvent to obtain intermediate B23. LC-MS: Measured value: 245.97 ([M+H] + ), theoretical value: 244.91.

[0203] Preparation of intermediate B24:

[0204] The synthesis of intermediate B24 was based on intermediate B21, except that diphenylamine was used instead of carbazole to obtain intermediate B24. LC-MS: Measured value: 566.11 ([M+H] + ), theoretical value: 565.11.

[0205] Preparation of intermediate C13:

[0206] The synthesis of intermediate C13 was based on intermediate C2, except that intermediate B24 was used instead of intermediate B2 to obtain intermediate C13. LC-MS: Measured value: 738.76 ([M+H] + ), theoretical value: 737.71.

[0207] Preparation of compound 74:

[0208] Compound 74 was prepared by referring to compound 129, except that intermediate C13 was used instead of intermediate C2 to obtain compound 74. LC-MS: Measured value: 754.34 ([M+H] + ), theoretical value: 753.27.

[0209] Example 15 Synthesis of Compound 228:

[0210]

[0211] Preparation of intermediate B23:

[0212] Add raw material A19 (2 mmol) to a dry pressure bottle, add 10 mL of dry toluene, then slowly add boron tribromide (2 mmol) dropwise at -10°C, slowly raise the temperature to 120°C and react for 18 hours. Drain the solvent to obtain intermediate B23. LC-MS: Measured value: 334.56 ([M+H] + ), theoretical value: 333.62.

[0213] Preparation of intermediate B24:

[0214] Intermediate B21 (5 mmol) was added to a dry three-necked flask, 30 mL of dry toluene was added, and the mixture was cooled to -78°C. N-butyl lithium (5 mmol) was slowly added dropwise, and the mixture was reacted at -78°C for 1 hour. The reaction mixture and raw material A20 (2.6 mmol) were simultaneously slowly added dropwise to a toluene solution of intermediate B23 (6 mmol), and the mixture was slowly heated to room temperature and reacted for 24 hours. After the reaction, two drops of methanol were added, and the mixture was extracted with dichloromethane solution. After drying over anhydrous sodium sulfate and filtering, the reaction solution was concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 500:1 as a developing solvent to obtain compound intermediate 24. LC-MS: Measured value: 694.10 ([M+H] +), theoretical value: 693.09.

[0215] Preparation of intermediate C14:

[0216] The synthesis of intermediate C14 was based on intermediate C2, except that intermediate B24 was used instead of intermediate B2 to obtain intermediate C14. LC-MS: Measured value: 866.56 ([M+H] + ), theoretical value: 865.69.

[0217] Preparation of compound 228:

[0218] Compound 228 was prepared by referring to compound 129, except that intermediate C14 was used instead of intermediate C2 to obtain compound 224. LC-MS: Measured value: 892.34 ([M+H] + ), theoretical value: 881.27.

[0219] The following representative compounds were also prepared according to the above synthesis method and their structural characteristics are shown in Table 1.

[0220] Table 1:

[0221]

[0222] The compounds of the present invention can be used as dopants for the light-emitting layer in light-emitting devices. The compounds prepared in the above examples of the present invention were tested for their physicochemical properties. Note: PLQY (fluorescence quantum yield) and FWHM (full width at half maximum) were measured in thin film form using a Horiba Fluorolog-3 series fluorescence spectrometer. The test results are shown in Table 2 below:

[0223] Table 2:

[0224]

[0225] As can be seen from the data in Table 2 above, the compound of the present invention has a high fluorescence quantum efficiency as a doping material, which is beneficial to improving the luminous efficiency of the device; at the same time, the spectral FWHM of the material is narrow, which can effectively improve the color purity of the device.

[0226] The technical effects and advantages of the present invention are demonstrated and verified by applying the compound of the present invention to an organic electroluminescent device to test its actual performance.

[0227] An organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer located between the two electrodes. The organic material layer can be divided into multiple regions, for example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0228] The anode material can be made of transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof. The cathode material can be made of metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof.

[0229] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and single-layer hole transport layers containing multiple compounds. The hole transport region can also be a multilayer structure comprising at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0230] The material of the hole transport region can be selected from but not limited to phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives, etc.

[0231] The light-emitting layer includes a luminescent dye (i.e., a dopant) that can emit light at different wavelengths, and may also include a host material. The light-emitting layer can be a monochromatic light-emitting layer that emits a single color, such as red, green, or blue. Multiple monochromatic light-emitting layers of different colors can be arranged in a planar pattern according to a pixel pattern, or they can be stacked together to form a multi-color light-emitting layer. When light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single-color light-emitting layer that can simultaneously emit different colors, such as red, green, and blue.

[0232] The electron transport region can be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region can also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0233] Combined with attachment Figure 2The process for preparing an organic electroluminescent device is as follows: an anode 2, a hole transport layer 3, an organic light-emitting layer 4, an electron transport layer 5, and a cathode 6 are sequentially deposited on a substrate 1, followed by encapsulation. The organic light-emitting layer 4 is formed by co-evaporation of a wide bandgap material source, an electron donor material source, an electron acceptor material source, and a resonant TADF material source.

[0234] Specifically, the method for preparing an organic electroluminescent device of the present invention comprises the following steps:

[0235] 1. The glass plate coated with the anode material was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0236] 2. Place the glass plate with the anode in a vacuum chamber and evacuate to 1×10 -5 ~9×10 -3 Pa, vacuum evaporating a hole injection material on the anode layer to form a hole injection layer at a rate of 0.1-0.5 nm / s;

[0237] 3. Vacuum evaporate the hole transport material on the hole injection layer to form a hole transport layer at a rate of 0.1-0.5 nm / s.

[0238] 4. Vacuum evaporate the electron blocking layer on the hole transport layer at a rate of 0.1-0.5 nm / s;

[0239] 5. Vacuum-depositing the organic light-emitting layer of the device on the electron blocking layer. The organic light-emitting layer materials include a host material and a TADF dye. Using a multi-source co-evaporation method, the evaporation rate of the host material, the evaporation rate of the sensitizer material, and the evaporation rate of the dye are adjusted to achieve a preset doping ratio of the dye.

[0240] 6. Vacuum-deposit a hole blocking layer on the organic light-emitting layer at a rate of 0.1-0.5 nm / s;

[0241] 7. Vacuum evaporating the electron transport material of the device on the hole blocking layer to form an electron transport layer at a rate of 0.1-0.5 nm / s;

[0242] 8. LiF was vacuum evaporated on the electron transport layer at a rate of 0.1-0.5 nm / s as the electron injection layer, and an Al layer was vacuum evaporated at a rate of 0.5-1 nm / s as the cathode of the device.

[0243] An embodiment of the present invention further provides a display device comprising the organic electroluminescent device described above. Specifically, the display device may be an OLED display, or any other display-capable product or component incorporating the display device, such as a television, digital camera, mobile phone, or tablet computer. The advantages of this display device over existing technologies are the same as those of the organic electroluminescent device described above, and are not further elaborated here.

[0244] The organic electroluminescent device of the present invention is further described below through specific examples.

[0245] Device Example 1

[0246] The structure of the organic electroluminescent device prepared in this embodiment is as follows:

[0247] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%4(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0248] Among them, the anode material is ITO; the hole injection layer material is HI, the total thickness is generally 5-30nm, and the present embodiment is 10nm; the hole transport layer material is HT, the total thickness is generally 5-500nm, and the present embodiment is 40nm; Host is the main material of the organic light-emitting layer with a wide band gap, the compound 4 of the present invention is a dye and the doping concentration is 2wt%, the thickness of the organic light-emitting layer is generally 1-200nm, and the present embodiment is 30nm; the electron transport layer material is ET, the thickness is generally 5-300nm, and the present embodiment is 30nm; LiF (0.5nm) and metal aluminum (150nm) are selected as the electron injection layer and cathode materials.

[0249] A DC voltage was applied to the organic electroluminescent device D1 prepared in this example, and the luminous flux of 10 cd / m 2 The characteristics of the light emission are: a light blue light emission with a wavelength of 480nm, a half-peak width of 27nm, CIE color coordinates (x, y) = (0.16, 0.27), and an external quantum efficiency EQE of 36.0% (driving voltage 2.6V). The electroluminescence spectrum is shown in the figure Figure 1 shown.

[0250] Device Example 2

[0251] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 129 instead of 4. The specific device structure is as follows:

[0252] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%129(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0253] The device performance of the organic electroluminescent device D2 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 485nm, a half-peak width of 33nm, CIE color coordinates (x, y) = (0.11, 0.32), and an external quantum efficiency EQE of 33.4% (driving voltage is 2.6V).

[0254] Device Example 3

[0255] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 110 instead of 4. The device structure is as follows:

[0256] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%110(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0257] The device performance of the organic electroluminescent device D3 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 490nm, a half-peak width of 26nm, CIE color coordinates (x, y) = (0.18, 0.33), and an external quantum efficiency EQE of 32.9% (driving voltage is 2.5V).

[0258] Device Example 4

[0259] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 113 instead of 4. The device structure is as follows:

[0260] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%113(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0261] The device performance of the organic electroluminescent device D4 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2The characteristics of the light emission are sky blue light emission with a wavelength of 502nm, a half-peak width of 28nm, CIE color coordinates (x, y) = (0.27, 0.42), and an external quantum efficiency EQE of 36.4% (driving voltage is 2.6V).

[0262] Device Example 5

[0263] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 195 instead of 4. The device structure is as follows:

[0264] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%195(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0265] The performance of the organic electroluminescent device D5 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 490nm, a half-peak width of 25nm, CIE color coordinates (x, y) = (0.11, 0.29), and an external quantum efficiency EQE of 33.4% (driving voltage is 2.6V).

[0266] Device Example 6

[0267] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 272 instead of 4. The device structure is as follows:

[0268] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%272(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0269] The performance of the organic electroluminescent device D6 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 492nm, a half-peak width of 32nm, CIE color coordinates (x, y) = (0.20, 0.47), and an external quantum efficiency EQE of 34.0% (driving voltage is 2.8V).

[0270] Device Example 7

[0271] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 281 instead of 4. The device structure is as follows:

[0272] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%281(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0273] The performance of the organic electroluminescent device D7 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 487nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.17, 0.33), and an external quantum efficiency EQE of 30.5% (driving voltage is 2.6V).

[0274] Device Example 8

[0275] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 231 instead of 4. The device structure is as follows:

[0276] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%231(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0277] The performance of the organic electroluminescent device D8 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 493nm, a half-peak width of 27nm, CIE color coordinates (x, y) = (0.148, 0.33), and an external quantum efficiency EQE of 31.1% (driving voltage is 2.5V).

[0278] Device Example 9

[0279] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 234 instead of 4. The device structure is as follows:

[0280] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%234(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0281] The performance of the organic electroluminescent device D9 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2The characteristics of the light emission are sky blue light emission with a wavelength of 495nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.23, 0.44), and an external quantum efficiency EQE of 33.6% (driving voltage is 2.6V).

[0282] Device Example 10

[0283] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 300 instead of 4. The device structure is as follows:

[0284] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%300(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0285] The performance of the organic electroluminescent device D10 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 500nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.29, 0.39), and an external quantum efficiency EQE of 33.4% (driving voltage is 2.7V).

[0286] Device Example 11

[0287] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 308 instead of 4. The device structure is as follows:

[0288] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%308(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0289] The performance of the organic electroluminescent device D11 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 516nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.27, 0.48), and an external quantum efficiency EQE of 34.2% (driving voltage is 2.7V).

[0290] Device Example 12

[0291] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 179 instead of 4. The device structure is as follows:

[0292] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%179(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0293] The device performance of the organic electroluminescent device D12 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 499nm, a half-peak width of 28nm, CIE color coordinates (x, y) = (0.15, 0.36), and an external quantum efficiency EQE of 31.5% (driving voltage is 2.6V).

[0294] Device Example 13

[0295] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 9 instead of 4. The device structure is as follows:

[0296] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%9(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0297] The device performance of the organic electroluminescent device D13 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 486nm, a half-peak width of 30nm, CIE color coordinates (x, y) = (0.17, 0.33), and an external quantum efficiency EQE of 30.2% (driving voltage is 2.6V).

[0298] Device Example 14

[0299] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 14 instead of 4. The device structure is as follows:

[0300] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%14(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0301] The device performance of the organic electroluminescent device D14 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2The characteristics of the light emission are sky blue light emission with a wavelength of 493nm, a half-peak width of 30nm, CIE color coordinates (x, y) = (0.21, 0.36), and an external quantum efficiency EQE of 34.8% (driving voltage is 2.6V).

[0302] Device Example 15

[0303] The preparation method is the same as that of device example 1, except that the dye in the light-emitting layer is replaced by 29 instead of 4. The device structure is as follows:

[0304] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%29(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0305] The performance of the organic electroluminescent device D15 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 499nm, a half-peak width of 25nm, CIE color coordinates (x, y) = (0.12, 0.39), and an external quantum efficiency EQE of 30.4% (driving voltage is 2.7V).

[0306] Device Example 16

[0307] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 77 instead of 4. The device structure is as follows:

[0308] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%77(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0309] The performance of the organic electroluminescent device D16 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 500nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.19, 0.32), and an external quantum efficiency EQE of 33.4% (driving voltage is 2.7V).

[0310] Device Example 17

[0311] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 181 instead of 4. The device structure is as follows:

[0312] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%181(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0313] The performance of the organic electroluminescent device D17 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are yellow light with a wavelength of 502nm, a half-peak width of 29nm, CIE color coordinates (x, y) = (0.18, 0.38), and an external quantum efficiency EQE of 30.7% (driving voltage is 2.6V).

[0314] Device Example 18

[0315] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 201 instead of 4. The device structure is as follows:

[0316] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%201(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0317] The device performance of the organic electroluminescent device D18 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 491nm, a half-peak width of 27nm, CIE color coordinates (x, y) = (0.13, 0.25), and an external quantum efficiency EQE of 32.7% (driving voltage is 2.5V).

[0318] Device Example 19

[0319] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 227 instead of 4. The device structure is as follows:

[0320] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%227(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0321] The performance of the organic electroluminescent device D19 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2The characteristics of the light emission are sky blue light emission with a wavelength of 489nm, a half-peak width of 26nm, CIE color coordinates (x, y) = (0.28, 0.30), and an external quantum efficiency EQE of 33.9% (driving voltage is 2.6V).

[0322] Device Example 20

[0323] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 229 instead of 4. The device structure is as follows:

[0324] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%229(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0325] The performance of the organic electroluminescent device D20 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 490nm, a half-peak width of 28nm, CIE color coordinates (x, y) = (0.24, 0.28), and an external quantum efficiency EQE of 33.9% (driving voltage is 2.6V).

[0326] Device Example 21

[0327] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 257 instead of 4. The device structure is as follows:

[0328] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%257(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0329] The device performance of the organic electroluminescent device D21 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 480nm, a half-peak width of 26nm, CIE color coordinates (x, y) = (0.12, 0.29), and an external quantum efficiency EQE of 34.0% (driving voltage is 2.6V).

[0330] Device Example 22

[0331] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 290 instead of 4. The device structure is as follows:

[0332] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%290(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0333] The device performance of the organic electroluminescent device D22 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 487nm, a half-peak width of 27nm, CIE color coordinates (x, y) = (0.23, 0.27), and an external quantum efficiency EQE of 31.4% (driving voltage is 2.6V).

[0334] Device Example 23

[0335] The preparation method is the same as that of device example 1, except that the number of dyes used in the light-emitting layer is replaced by 2. The device structure is as follows:

[0336] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%2(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0337] The device performance of the organic electroluminescent device D23 prepared in this example is as follows: DC voltage is applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 469nm, a half-maximum width of 31nm, CIE color coordinates (x, y) = (0.23, 0.29), and an external quantum efficiency EQE of 29.4% (driving voltage is 2.7V).

[0338] Device Example 24

[0339] The preparation method is the same as that of device example 1, except that the dye used in the light-emitting layer is replaced by 74 instead of 4. The device structure is as follows:

[0340] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%74(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0341] The device performance of the organic electroluminescent device D24 prepared in this example is as follows: DC voltage is applied and the 10 cd / m 2The characteristics of the light emission are sky blue light emission with a wavelength of 465nm, a half-peak width of 31nm, CIE color coordinates (x, y) = (0.23, 0.29), and an external quantum efficiency EQE of 28.4% (driving voltage is 2.6V).

[0342] Device Example 25

[0343] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by 228 instead of 4. The device structure is as follows:

[0344] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%228(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0345] The performance of the organic electroluminescent device D25 prepared in this example was measured as follows: a DC voltage was applied and the luminous flux of 10 cd / m 2 The characteristics of the light emission are sky blue light emission with a wavelength of 469nm, a half-peak width of 31nm, CIE color coordinates (x, y) = (0.23, 0.33), and an external quantum efficiency EQE of 30.4% (driving voltage is 2.7V).

[0346] Comparative Device Example 1

[0347] The preparation method is the same as that of device example 1, except that the compound 4 of the present invention used in the light-emitting layer is replaced by the compound P1 in the prior art. The specific device structure is as follows:

[0348] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%P1(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)The device performance results of the organic electroluminescent device DD1 prepared in this example are as follows: when a DC voltage is applied and the characteristics of the luminescence at 10cd / m2 are measured, blue light with a wavelength of 469nm, a half-peak width of 27nm, CIE color coordinates (x, y) = (0.12, 0.18), and an external quantum efficiency EQE of 29.3% can be obtained (driving voltage is 3.6V).

[0349] Comparative Device Example 2

[0350] The preparation method is the same as that of device example 2, except that the compound 1 of the present invention used in the light-emitting layer is replaced by the compound P2 in the prior art. The specific device structure is as follows:

[0351] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%P2(30nm) / HBL(10nm)ET(30nm) / LiF(0.5nm) / Al(150nm)

[0352] The device performance of the organic electroluminescent device DD2 prepared in this example is measured as follows: DC voltage is applied and the 10 cd / m 2 The characteristics of the light emission are blue light emission with a wavelength of 466nm, a half-maximum width of 30nm, CIE color coordinates (x, y) = (0.13, 0.16), and an external quantum efficiency EQE of 18.4% (driving voltage 3.3V).

[0353] The structural formulas of the various organic materials used in the above embodiments are as follows:

[0354]

[0355]

[0356] The specific performance data of the organic electroluminescent devices D1 to D25 and devices DD1 and DD2 prepared in the above device embodiments are shown in Table 3 below.

[0357] Table 3:

[0358]

[0359]

[0360] The above experimental data show that the compound of the present invention greatly simplifies the introduction process of B by introducing a BN polar covalent bond into the B and N molecular skeletons with a multiple resonance effect (MR), while retaining the MR effect when B and N are in the para position, and expanding the narrow-band emission molecular skeleton system. Compared with Comparative Examples 1 and 2, the series of materials of the present invention have a simpler and more efficient synthesis, a reaction yield of more than 90%, and a half-maximum width (FWHM) of the molecular fluorescence spectrum of only 26-32nm, PLQY> 90%, with high brightness, greatly enriching the material system of multiple resonance-thermally activated delayed fluorescence, and having good application prospects. It is worth emphasizing that, compared with Comparative Example 2, the compound of the present invention retains a substituent on the para position of the skeleton center benzene ring connected to the nitrogen atom in the compound of the present invention, which can be an alkyl substituent or an aryl substituent, which can make the reaction more selective and generate a double boron product in high yield. If there is no such substituent, the reaction can only generate a unilateral boron product.

[0361] Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above-described embodiments. It should be understood that, guided by the concept of the present invention, those skilled in the art may make various modifications and improvements, and the appended claims summarize the scope of the present invention. Obviously, the above-described embodiments are merely examples for the purpose of clear explanation and are not limitations on the implementation methods. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. However, obvious changes or modifications derived therefrom are still within the scope of protection created by the present invention.

Claims

1. A luminescent material, as shown in the following formula (1): In formula (1), the dotted line represents connection or non-connection; Y stands for N or B; Ring A, Ring B, Ring C, Ring D, Ring E, and Ring F are each independently selected from a benzene ring or a pyridine ring; n1, n2, n3 are all 1, X 1 、X 2 and X 3 At the same time, it is a single bond; Or, n1 and n3 are both 1, n2 is 0 or 1, X 1 and X 3 At the same time, X 2 CR1R2, NR3, BR4, SiR5R6, O, S; The R1, R2, R3, R4, R5, and R6 are independently selected from one of the following groups: a C1-C36 chain alkyl group or a C6-C60 monocyclic aromatic group; R a 、R b 、R c 、R d 、R e 、R f Each independently represents a substituent up to the maximum allowed number of substituents, and is independently selected from hydrogen, deuterium, cyano, halogen, or one of the following substituted or unsubstituted groups: C1-C6 chain alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 thioalkoxy, C6-C20 arylamino, C3-C20 heteroarylamino, C6-C30 aryl, C6-C30 aryloxy, C5-C30 heteroaryl; R g One selected from the following substituted or unsubstituted groups: C1-C6 chain alkyl, C6-C30 aryl, C5-C30 single heteroaryl; When the above R1, R2, R3, R4, R5, R6, a 、R b 、R c 、R d 、R e 、R f 、R g When substituents are present, the substituents are independently selected from one or a combination of two of deuterium, halogen, C1-C30 chain alkyl, C6-C60 monocyclic aromatic group, and C5-C60 monocyclic heteroaromatic group.

2. The luminescent material according to claim 1, characterized in that It has a structure as shown in any one of the following formulas (2), (3), (4), (5), (6) or (7): In formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7), X 1 、X 2 、X 3 、n1、n2、n3、R a 、R b 、R c 、R d 、R e 、R f and R g The definitions of are the same as those in formula (1).

3. The luminescent material according to claim 1, characterized in that It has a structure as shown in the following formula (8) or formula (9): In formula (8) and formula (9), the dotted line represents the connection; X 1 、X 2 、X 3 、n1、n2、n3、R a 、R c 、R d 、R e 、R f and R g The definitions of are the same as those in formula (1).

4. The luminescent material according to any one of claims 1 to 3, characterized in that The R a 、R b 、R c 、R d 、R e 、R f are independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-methylbutyl, trifluoromethyl, pentafluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, tetraphenyl, pentacene, benzopyrenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiophene, phenyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthioimidazolyl, phenanthioimidazolyl, pyridoimidazolyl, pyrazinoimidazole 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl or methoxy.

5. The luminescent material according to claim 4, characterized in that The R g phenyl, naphthyl, anthracenyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, neohexyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrenyl, fluoranthenyl, tetracenyl, pentacene, benzopyrenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl The present invention also includes one of quinolinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, triarylamine, fluorophenyl, methylphenyl, and trimethylphenyl.

6. A luminescent material selected from the following specific structural compounds:

7. Use of the luminescent material according to any one of claims 1 to 6, characterized in that: The application is as a functional material in organic electronic devices, including organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic paper; the luminescent material is used as a light-emitting layer material in the organic electroluminescent device.

8. An organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, characterized in that: The organic layer comprises at least one luminescent material according to any one of claims 1 to 6.

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