An organic luminescent compound containing dibenzoheterocycloheptanone, preparation method and application thereof

Abstract

The present invention provides an organic light-emitting compound containing dibenzoheterocycloheptanone, a preparation method and an application thereof. The material structure of the organic light-emitting compound containing dibenzoheterocycloheptanone of the present invention is single, the molecular weight is determined, it is easy to purify, the reproducibility of multiple synthesis is good, and it is easy to study the relationship between structure and performance, and the compound has a low sublimation temperature and decomposition temperature, a stable film morphology, and is easy to prepare devices. The compound of the present invention can effectively regulate the conjugation length and the color of the light emission of the material by changing the chemical structure of the connection, and by changing the modifying group on the aromatic structure, the physical properties of the organic light-emitting compound containing dibenzoheterocycloheptanone of the present invention and the performance of the optoelectronic device based thereon can be further improved.

Description

Technical Field

[0001] The invention belongs to the technical field of electroluminescent materials, and specifically relates to an organic luminescent compound containing dibenzoheterocycloheptanone, a preparation method and application thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) have received great attention from academia and industry due to their advantages such as full solid-state, self-luminescence, wide viewing angle, fast response, lightness, and flexibility. They have become the mainstream direction of the development of the display industry and play an important role in the new generation of flat-panel displays and solid-state lighting. In the entire OLED industry chain, organic light-emitting materials have always played a vital role and are one of the fields with the highest technical barriers. Thermally activated delayed fluorescence materials (TADF) have become a hot topic of research at home and abroad because they can theoretically achieve 100% exciton utilization and avoid the use of high-cost precious metals. In recent years, due to the potential application of circularly polarized light in 3D display, information processing, quantum communication, biological imaging and other fields, organic circularly polarized light-emitting devices and detection devices have received great attention from scientists. In these devices, chiral organic optoelectronic materials are the core and foundation.

[0003] However, the skeletons of most circularly polarized luminescent molecules currently used in organic optoelectronic devices are based on chiral cyclohexanediamine units and chiral biaryl compounds, while organic luminescent small molecules based on dibenzoheterocycloheptanone are rarely reported. This type of organic small molecule has a single structure, a certain molecular weight, and a simple purification step, and can be used in organic optoelectronic devices including organic light-emitting diodes.

[0004] Based on this, the present invention provides an organic light-emitting compound containing dibenzoheterocycloheptanone, a preparation method and an application thereof, which can further improve the ability of the material to balance carriers, thereby improving the efficiency and stability of the device. Summary of the invention

[0005] In order to overcome the deficiencies of the prior art, the present invention provides an organic light-emitting compound containing dibenzoheterocycloheptanone, a preparation method and an application thereof, so as to solve the problem in the prior art of improving the ability of the organic light-emitting compound to balance carriers, thereby improving the efficiency and stability of the device.

[0006] One embodiment of the present invention provides an organic light-emitting compound containing dibenzoheterocycloheptanone, wherein the organic light-emitting compound containing dibenzoheterocycloheptanone is represented by the following general structural formula:

[0007]

[0008] in,

[0009] X is independently selected from oxygen atom, sulfur atom, nitrogen atom, silicon atom;

[0010] A1 is independently selected from phenyl, aromatic amino or methyl;

[0011] R1 is independently selected from C1-C16 alkyl;

[0012] R2 is independently selected from C1-C16 alkyl;

[0013] A2 is selected from one or more combinations of electron-donating vinylene groups, ethynylene groups, aromatic rings composed of carbon and hydrogen atoms, aromatic heterocycles composed of carbon, nitrogen, hydrogen atoms, aromatic heterocycles composed of carbon, nitrogen, oxygen, hydrogen atoms, aromatic heterocycles composed of carbon, nitrogen, sulfur, hydrogen atoms, aromatic heterocycles composed of carbon, nitrogen, silicon, hydrogen atoms, alkyl-substituted conjugated units, alkoxy-substituted conjugated units, or conjugated units simultaneously substituted with alkyl and alkoxy groups.

[0014] Specifically, the organic light-emitting compound containing dibenzoheterocycloheptanone uses a novel dibenzoheterocycloheptanone as a skeleton unit. By changing its heterocyclic atoms, two-side connecting units and their number, the molecular weight, π conjugation and intramolecular charge transfer properties of the material can be adjusted, thereby effectively realizing the preparation of high-efficiency circularly polarized light-emitting materials.

[0015] Furthermore, the raw material used to synthesize the organic light-emitting compound containing dibenzoheterocycloheptanone is selected from the following structures:

[0016]

[0017] in,

[0018] Y is independently selected from a chlorine atom, a bromine atom, and an iodine atom.

[0019] Furthermore, the Y is a chlorine atom.

[0020] Furthermore, the organic light-emitting compound containing dibenzoheterocycloheptanone is selected from the following structures:

[0021]

[0022] The present invention also provides a method for preparing an organic light-emitting compound containing dibenzoheterocycloheptanone, characterized in that the method for preparing an organic light-emitting compound containing dibenzoheterocycloheptanone comprises the following steps:

[0023] The raw materials for synthesizing the organic luminescent compound containing dibenzoheterocycloheptanone and the substance containing an aromatic group of active hydrogen are dissolved in a solvent, heated, and reacted to obtain the organic luminescent compound containing dibenzoheterocycloheptanone.

[0024] Furthermore, the solvent is selected from one or more of toluene, chloroform and o-xylene.

[0025] Preferably, the solvent is toluene.

[0026] Furthermore, the substance containing an active hydrogen aromatic group is selected from acridine, spiroacridine-thioxanthene, phenoxazine, carbazole, and tert-butylcarbazole.

[0027] Furthermore, the reaction is selected from one of Suzuki coupling, Buchwald-Hartwig coupling or copper-catalyzed amination of aryl halides.

[0028] The invention also provides an organic electroluminescent device, comprising the organic luminescent compound containing dibenzoheterocycloheptanone.

[0029] The organic luminescent compound containing dibenzoheterocycloheptanone, the preparation method and the application provided by the present invention have the following advantages:

[0030] Beneficial effects:

[0031] 1. The material structure of the organic light-emitting compound containing dibenzoheterocycloheptanone of the present invention is simple, the molecular weight is determined, it is easy to purify, the reproducibility of multiple syntheses is good, and it is easy to study the relationship between structure and performance. In addition, the compound has a low sublimation temperature and decomposition temperature, has good solubility and film-forming properties in common solvents, and has a stable film morphology, which is convenient for preparing devices. The compound of the present invention can effectively regulate the conjugation length and luminescent color of the material by changing the connected chemical structure. At the same time, by changing the modifying group on the aromatic structure, the physical properties of the organic light-emitting compound containing dibenzoheterocycloheptanone of the present invention and the performance of the optoelectronic device based thereon can be further improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a spectrum diagram of the organic electroluminescent blue light device of Application Example 1;

[0033] Figure 2 The current density-voltage-brightness relationship curve of the organic electroluminescent blue light device of Application Example 1;

[0034] Figure 3 The relationship curve between external quantum efficiency and current density of the organic electroluminescent blue light emitting device of Application Example 1 is shown;

[0035] Figure 4 This is a graph showing the relationship between external quantum efficiency and current density for comparative application example 1. DETAILED DESCRIPTION

[0036] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0037] It should be noted that, in the examples of the present invention, the preparation methods of the final products of compounds M1-M17 containing dibenzoheterocycloheptanone are all carried out independently and without interfering with each other.

[0038] Example 1

[0039] Synthesis of Compound M1 Containing Dibenzoheterocycloheptanone

[0040]

[0041] 3 mmol of P1 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under reflux for 24 hours. After cooling, the mixture was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain a compound M1 containing dibenzoheterocycloheptanone.

[0042] The yield of compound M1 was 70%.

[0043] Example 2

[0044] Synthesis of Compound M2 Containing Dibenzoheterocycloheptanone

[0045]

[0046] 3mmol of P1, 3.5mmol of phenoxazine, 100mL of toluene, 60mg of palladium acetate, 0.5mmol, 0.11g of tri-tert-butyl phosphine and 0.75g of potassium carbonate were added, and the mixture was stirred under heating reflux for 24h. After cooling, the mixture was poured into 200mL of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain a compound M2 containing dibenzoheterocycloheptanone.

[0047] The yield of compound M2 was 75%.

[0048] Example 3

[0049] Synthesis of Compound M3 Containing Dibenzoheterocycloheptanone

[0050]

[0051] 3 mmol of P1, 3.3 mmol of carbazole, 0.23 g of CuI, 0.55 g of K2CO3, 0.1 g of C 18O6 was dissolved in DMPU, heated to 180°C, reacted for 24 hours, extracted with dichloromethane, dried, extracted with chloroform, separated and purified by silica gel column chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M3 containing dibenzoheterocycloheptanone.

[0052] The yield of compound M3 was 70%.

[0053] Example 4

[0054] Synthesis of Compound M4 Containing Dibenzoheterocycloheptanone

[0055]

[0056] 3 mmol of P1, 3.3 mmol of tert-butylcarbazole, 0.23 g of Cu, 0.55 g of K2CO3, 0.1 g of C 18 O6 was dissolved in DMPU, heated to 180°C, reacted for 24 hours, extracted with dichloromethane, dried, extracted with chloroform, separated and purified with a silica gel column to obtain a white solid, which was then dried and sublimated under vacuum to obtain a compound M4 containing dibenzoheterocycloheptanone.

[0057] The yield of compound M4 was 71%.

[0058] Example 5

[0059] Synthesis of Compound M5 Containing Dibenzoheterocycloheptanone

[0060]

[0061] 3 mmol of P1 and 3.5 mmol of phenothiazine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified with a silica gel column, and then dried and sublimated under vacuum to obtain compound M5 containing dibenzoheterocycloheptanone.

[0062] The yield of compound M5 was 71%.

[0063] Example 6

[0064] Synthesis of Compound M6 Containing Dibenzoheterocycloheptanone

[0065]

[0066] 3 mmol of P1 and 3.5 mmol of spiroacridine-thioxanthene were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain a compound M6 containing dibenzoheterocycloheptanone.

[0067] The yield of compound M6 was 81%.

[0068] Example 7

[0069] Synthesis of Compound M7 Containing Dibenzoheterocycloheptanone

[0070]

[0071] 3 mmol of P2 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M7 containing dibenzoheterocycloheptanone.

[0072] The yield of compound M7 was 68%.

[0073] Example 8

[0074] Synthesis of Compound M8 Containing Dibenzoheterocycloheptanone

[0075]

[0076] 3 mmol of P2 and 3.5 mmol of phenoxazine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified with a silica gel column, and then dried and sublimated under vacuum to obtain compound M8 containing dibenzoheterocycloheptanone.

[0077] The yield of compound M8 was 74%.

[0078] Example 9

[0079] Synthesis of Compound M9 Containing Dibenzoheterocycloheptanone

[0080]

[0081] 3 mmol of P2, 3.3 mmol of carbazole, 0.23 g of CuI, 0.55 g of K2CO3, 0.1 g of C 18 O6 was dissolved in DMPU, heated to 180°C, reacted for 24 hours, extracted with dichloromethane, dried, extracted with chloroform, separated and purified by silica gel column chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M9 containing dibenzoheterocycloheptanone.

[0082] The yield of compound M9 was 69%.

[0083] Example 10

[0084] Synthesis of Compound M10 Containing Dibenzoheterocycloheptanone

[0085]

[0086] 3 mmol of P2, 3.3 mmol of tert-butyl carbazole, 0.23 g of CuI, 0.55 g of K2CO3, 0.1 g of C 18 O6 was dissolved in DMPU, heated to 180°C, reacted for 24 hours, extracted with dichloromethane, dried, extracted with chloroform, separated and purified by silica gel column chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M10 containing dibenzoheterocycloheptanone.

[0087] The yield of compound M10 was 71%.

[0088] Embodiment 11

[0089] Synthesis of Compound M11 Containing Dibenzoheterocycloheptanone

[0090]

[0091] 3 mmol of P2 and 3.5 mmol of phenothiazine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M11 containing dibenzoheterocycloheptanone.

[0092] The yield of compound M11 was 71%.

[0093] Example 12

[0094] Synthesis of Compound M12 Containing Dibenzoheterocycloheptanone

[0095]

[0096] 3 mmol of P2 and 3.5 mmol of spiroacridine-thioxanthene were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M12 containing dibenzoheterocycloheptanone.

[0097] The yield of compound M12 was 81%.

[0098] Embodiment 13

[0099] Synthesis of Compound M13 Containing Dibenzoheterocycloheptanone

[0100]

[0101] 3 mmol of P3 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixture was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M13 containing dibenzoheterocycloheptanone.

[0102] The yield of compound M13 was 70%.

[0103] Embodiment 14

[0104] Synthesis of Compound M14 Containing Dibenzoheterocycloheptanone

[0105]

[0106] 3 mmol of P4 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried with anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified with a silica gel column, and then dried and sublimated under vacuum to obtain compound M14 containing dibenzoheterocycloheptanone.

[0107] The yield of compound M14 was 69%.

[0108] Embodiment 15

[0109] Synthesis of Compound M15 Containing Dibenzoheterocycloheptanone

[0110]

[0111] 3 mmol of P5 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M15 containing dibenzoheterocycloheptanone.

[0112] The yield of compound M15 was 71%.

[0113] Example 16

[0114] Synthesis of Compound M16 Containing Dibenzoheterocycloheptanone

[0115]

[0116] 3 mmol of P6 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixed solution was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain a compound M16 containing dibenzoheterocycloheptanone.

[0117] The yield of compound M16 was 71%.

[0118] Embodiment 17

[0119] Synthesis of Compound M17 Containing Dibenzoheterocycloheptanone

[0120]

[0121] 3 mmol of P7 and 3.5 mmol of acridine were added to 100 mL of toluene, and 60 mg of palladium acetate, 0.5 mmol, 0.11 g of tri-tert-butyl phosphine and 0.75 g of potassium carbonate were added. The mixture was stirred and reacted under heating reflux for 24 hours. After cooling, the mixture was poured into 200 mL of water, and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed after separation. The white solid was separated and purified by silica gel chromatography to obtain a white solid, which was then dried and sublimated under vacuum to obtain compound M17 containing dibenzoheterocycloheptanone.

[0122] The yield of compound M17 was 72%.

[0123] Comparative Example 1

[0124] A method for preparing an organic light-emitting compound. The difference between this comparative example and Example 7 is that P7 is replaced by achiral brominated dibenzophenone. The prepared organic light-emitting compound N1 is shown in the figure below. The other steps and materials are the same as those in Example 7.

[0125]

[0126] Application Example 1

[0127] The compound M7 in Example 7 of the present invention and the compound N1 prepared in Comparative Example 1 were applied to the light-emitting layer in an OLED device to further illustrate the actual technical effect of the present invention.

[0128] In Example 7 of the present invention, M7 is used as the guest material of the light-emitting layer, and the prepared device OLED structure is: ITO / HATCN (5nm) / TAPC (30nm) / TCTA (10nm) / mCBP (10nm) / M7-doped PPF (M7 accounts for 15wt% of this layer) (20nm) / DPEPO (10nm) / TmPyPB (40nm) / LiF (1nm) / Al (150nm).

[0129] Figure 1 This is a spectrum diagram of the organic electroluminescent blue light device of Application Example 1; Figure 2 The current density-voltage-brightness relationship curve of the organic electroluminescent blue light device of Application Example 1; Figure 3 This is a curve diagram of the relationship between external quantum efficiency and current density of the organic electroluminescent blue light device of Application Example 1.

[0130] Comparative application example 1

[0131] The compound prepared in Comparative Example 1 is used as the guest material of the light-emitting layer, and the structure of the prepared device OLED is: ITO / HATCN (5nm) / TAPC (30nm) / TCTA (10nm) / mCBP (10nm) / N1-doped PPF (N1 accounts for 15wt% of the layer) (20nm) / DPEPO (10nm) / TmPyPB (40nm) / LiF (1nm) / Al (150nm).

[0132] Figure 4 This is a graph showing the relationship between external quantum efficiency and current density for comparative application example 1.

[0133] Test Case

[0134] In Application Example 1 and Comparative Application Example 1, OLED devices were prepared respectively, and a positive bias voltage was applied between the ITO and metal electrodes, and the characteristics of the devices were tested under different currents.

[0135] The test data of the organic electroluminescent device prepared above are shown in Table 1 below:

[0136] Table 1 Device application example 1 and comparative application example 1 data

[0137]

[0138] From Table 1 and Figure 1-4 It can be seen that adding a compound containing dibenzoheterocycloheptanone as the light-emitting layer in the OLED device can achieve high brightness and small efficiency roll-off in the device, improve the device's ability to balance carriers, thereby improving the efficiency and stability of the device, thereby achieving high-efficiency performance in the organic electroluminescent device. In contrast, the stability of the device prepared by N1 in Application Example 1 is significantly reduced, and the same technical effect as in Application Example 1 cannot be achieved.

[0139] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0140] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. An organic light-emitting compound containing dibenzoheterocycloheptanone, characterized in that: The organic light-emitting compound containing dibenzoheterocycloheptanone has the following structure: 。 2. The method for preparing the organic light-emitting compound containing dibenzoheterocycloheptanone according to claim 1, characterized in that: The reaction equation for preparing the organic light-emitting compound containing dibenzoheterocycloheptanone is: 。 3. An organic electroluminescent device, characterized in that: The organic light-emitting compound comprising dibenzoheterocycloheptanone as described in claim 1.

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