Carboxylate modified macrocyclic molecule as well as preparation method and application thereof

Abstract

The invention discloses a carboxylic ester modified macrocyclic molecule as well as a preparation method and application thereof, and relates to the technical field of organic materials and electroluminescent devices. The macrocyclic molecule comprises a molecular structural formula I and a molecular structural formula II, macrocycles of the macrocyclic molecule respectively contain 8 1, 4-para-phenylene groups and 10 1, 4-para-phenylene groups, and R in the structure can be selected variously; the synthesis method comprises the following steps: step-by-step connection of carboxylic ester monomers, template-guided cyclization, intramolecular ring-closing reaction, palladium catalytic reaction and the like. Devices based on the molecule comprise an electronic device, a hole device and an OLED (Organic Light Emitting Diode) device which all comprise functional thin film layers, and the preparation methods are diversified; the molecules and the device have outstanding photoelectric properties, and can reduce intermolecular acting force, reduce pi-pi stacking, improve solubility, reduce the turn-on voltage of the device and regulate and control the light-emitting color; and through application in different devices, a new solution is provided for related fields, and the method has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic materials and electroluminescent devices, in particular to a class of macrocyclic molecules of modified carboxylic acid esters and a preparation method and application thereof. Background Art

[0002] OLED is a diode that uses the light-emitting property of organic materials when current is passed through it. The device structure has active and passive types. The active type uses thin film transistors to control the current. Unlike traditional liquid crystal displays, it does not require a backlight source and has the advantages of being thinner, lighter, higher contrast, faster response, wider viewing angle, and lower power consumption. It is widely used in display technology.

[0003] The basic structure of an OLED device includes a transparent conductive ITO (indium tin oxide) electrode, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), etc. Among them, an organic light-emitting material layer is sandwiched between the anode and the cathode. After the charge is injected into the organic light-emitting material, the electrons and holes recombine to generate light. The manufacturing process of OLED is simple and only requires low voltage driving, which gives it a huge advantage in flat-panel display applications. In recent years, the performance of OLED devices has been significantly improved by regulating the molecular structure of materials, optimizing device structure and process, and introducing new materials and technologies. In particular, the introduction of new materials has met consumers' new demands for display technology and promoted the development and application of OLED technology. The key to optimizing OLED devices is to improve the luminous efficiency of materials, charge injection balance and stability, and reduce the power consumption of devices, thereby continuously improving their application performance in various display devices.

[0004] The photophysical properties of the end-to-end cyclic biphenyl structure are more prominent than those of the linear biphenyl structure commonly used in OLEDs, and are similar to the properties of carbon nanotubes. In solution, film and crystal forms, more prominent photophysical properties are exhibited, and the cyclic structure and π-conjugated system have also attracted increasing interest in the field of organic semiconductors. Theoretical methods predict that a series of carbon nanorings and derivatives have high electron mobility and great potential in electroluminescent materials; therefore, the present invention proposes a class of macrocyclic molecules modified with carboxylic acid esters, and a preparation method and application thereof. Summary of the invention

[0005] The object of the present invention is to provide a class of organic materials containing carboxylic acid ester macrocycles, which can be used in light-emitting devices or electroluminescent devices, especially organic light-emitting diodes (OLEDs); the device includes a light-emitting layer and at least two electrodes; the present invention also relates to an apparatus comprising the electronic device, hole device and / or OLED to solve the problems raised in the above background.

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical solution: a type of macrocyclic cyclic molecule of modified carboxylic acid ester, including molecular structural formula I, the molecular structural formula is: ; Furthermore, the macrocycle of the molecular structural formula I contains 8 benzene rings, and the molecular structural formula I includes R, wherein R is independently selected from hydrogen, substituted or unsubstituted C1 to C 30 Alkyl, substituted or unsubstituted C1~C 30 Heteroatoms (one of N, S, O, P, Se, Si, B) alkyl, substituted or unsubstituted C1~C 30 One of the aromatic alkyl groups; n in the molecular structure formula can take an integer value of 0 to 2.

[0007] Furthermore, a type of macrocyclic cyclic molecule modified with carboxylic acid ester also includes a molecular structural formula II, the molecular structure of which is: ; A method for preparing a type of macrocyclic cyclic molecule modified with carboxylic acid esters, the method comprising the following steps; Preparation of intermediate 1: Under the protection of inert gas, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI, and Et3N and THF solvent system are subjected to Sonogashira-Hagihara coupling reaction, and after separation and purification, the reaction is carried out in a mixed solvent of potassium carbonate, methanol and THF (under the protection of inert gas) to obtain intermediate 1; Preparation of intermediate 2: Under the protection of inert gas, 2,5-dibromo-1,4-diiodobenzene, intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene are subjected to Sonogashira-Hagihara coupling reaction, and intermediate 2 is obtained after separation and purification, and intermediate 2 is one of intermediates V; Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, THF and H2O are subjected to Suzuki-Miyaura coupling reaction; after separation and purification, they are placed in a mixture of HCl, SnCl2·2H2O, and the reaction temperature is low temperature, dry THF, and after separation and purification, molecular structure I is obtained; the synthesis route is as follows:

[0008] Furthermore, the Sonogashira-Hagihara coupling reaction was carried out in a solvent system of Et3N (12.5 mL) and THF (50 mL).

[0009] Further, intermediate 2 is a kind of intermediate V, and its molecular structure is: ; n is 0, 1, or 2 respectively.

[0010] When n is 1 and R is methyl, the synthesis steps of intermediate 2 are as follows; Preparation of 2,5-dibromo-1,4-diiodobenzene: Place p-dibromobenzene (12.50 g, 53.45 mmol) in a dry round-bottom flask (500 mL) filled with concentrated sulfuric acid (160 mL), and add iodine (51.80 g, 204.10 mmol) in batches; seal the flask under negative pressure, heat to 125-135 °C, and stir to react for 2 days; after cooling to room temperature, pour the mixture into ice water to quench; filter the solid precipitate, and wash it repeatedly with saturated sodium bisulfite solution and sodium bicarbonate solution respectively; the crude product is separated by flash column chromatography (CH2Cl2) to obtain a white compound 2,5-dibromo-1,4-diiodobenzene (20.46 g, 78%), or recrystallized from hot benzene solution; Preparation of dimethyl 4,4'-((2,5-dibromo-1,4-phenylene)bis(acetylene-2,1-diyl))dibenzoate: 2,5-dibromo-1,4-diiodobenzene (4.4 g, 9.02 mmol), intermediate 1 (3.10 g, 19.35 mmol), diisopropylamine (15 mL) and toluene (45 mL) were added to a round-bottom flask (100 mL) and purged with argon for 15 minutes. Pd(PPh3)2Cl2 (316 mg, 0.45 mmol) and CuI (172 mg, 0.90 mmol) were added and the mixture was purged with argon for 15 minutes again; the reaction was stirred at room temperature for 12 hours; the product was collected by vacuum filtration and washed with Hexane and CH3OH solvents until it was colorless; the product was then placed in a small amount of DCM and stirred, and dried by vacuum filtration to obtain intermediate 2 (4.03 g, 81%). The synthetic route is as follows: ;

[0011] Further, when preparing the molecular structure II: intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF and H2O, through Suzuki-Miyaura coupling reaction; after separation and purification, it is placed in a mixture of HCl, SnCl2·2H2O, and can be reacted at room temperature in an ice-water bath, dry THF, and after separation and purification, the molecular structure II is obtained; the synthesis route is as follows:

[0012] An application of a type of macrocyclic cyclic molecule modified with a carboxylic acid ester as described above, wherein the macrocyclic cyclic molecule is used to prepare a light-emitting device, wherein the light-emitting device includes an electronic device, a hole device and an OLED device, and the electronic device, the hole device and the OLED device all include a functional thin film layer.

[0013] The beneficial effects of the present invention are as follows: (1) In the technical solution of the present application, compared with linear aromatic conjugation, the skeleton of the organic cyclic π conjugated compound has a strong electron transfer ability and more outstanding photoelectric performance. The cyclic skeleton is connected with a group with electron ability, so that the compound has a bipolar structure, which is conducive to the transmission and recombination of electrons and holes. The introduction of groups in the macrocycle increases the electron transfer channel of the macrocycle, which can improve the luminescence efficiency of the device containing it; at the same time, the structure can reduce the intermolecular force and reduce the intermolecular π-π stacking; the introduction of flexible functional groups can improve the solubility of molecules, improve the solubility of luminescent functional films, and reduce defects in the film; carbon nanorings are ultra-short structures of carbon nanotubes and have the properties of carbon nanotubes; in addition, organic compounds can also reduce the turn-on voltage of the device, and the turn-on voltage is also affected by the modified functional groups, which can adjust the luminous color of OLED devices.

[0014] (2) The present invention obtains a macrocyclic cyclic compound of methyl carboxylate through molecular design; the macrocyclic cyclic compound of methyl carboxylate provided by the present invention DP

[10] CPP can be used as an electron transport material for OLED light-emitting devices, and DP[8]CPP can be used as a hole transport material for OLED light-emitting devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 For DP

[10] CPP 1 H NMR spectra; Figure 2 For intermediate 2 1 H NMRR graph; Figure 3 Schematic diagram of the electronic device structure Figure 1 ; Figure 4 Schematic diagram of the electronic device structure Figure 2 ; Figure 5 Schematic diagram of the hole device structure Figure 1 ; Figure 6 Schematic diagram of the hole device structure Figure 2 ; Figure 7 Schematic diagram of the structure of OLED device Figure 1 ; Figure 8 Schematic diagram of the structure of OLED device Figure 2 ; Fig. 9 For DP[8]CPP electronic devices J 1 / 2 - V and fitted curve graph; Fig.10 The hole device of DP[8]CPP J 1 / 2 - V and fitted curve graph; Fig.11 For DP

[10] CPP electronic devices J 1 / 2 - V and fitted curve graph; Fig.12 The hole device of DP

[10] CPP J 1 / 2 - V and fitted curve graph; Fig.13 Schematic diagram of OLED device and energy level based on DP[8]CPP / DP

[10] CPP molecules; Fig.14 The physical pictures of the OLED device structures of DP[8]CPP and DP

[10] CPP; Fig.15 is a graph of current density and voltage for DP[8]CPP and DP

[10] CPP; Fig.16 is a graph of brightness and voltage of DP[8]CPP and DP

[10] CPP; Fig.17 is a graph of the external fluorescence quantum efficiency and voltage of DP[8]CPP and DP

[10] CPP; Fig.18 It is a schematic diagram of the three-dimensional structure of molecular formula I and molecular formula II; DETAILED DESCRIPTION

[0016] In order to make the invention purpose, technical scheme and beneficial technical effect of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application, not for limiting the present application. In order to describe the present invention in more detail, the following examples are given, but are not limited thereto, as representative, and should not be exhaustive.

[0017] The terms "cyclic" and "macrocyclic" mentioned in the present invention refer to an Armchair-type macrocyclic structure composed of multiple para-phenylene groups; "a", "a type" and "the" all refer to one or more molecules of the compound, rather than being limited to a single molecule of the compound; Example 1

[0018] A type of macrocyclic cyclic molecule modified with carboxylic acid esters includes a molecular structural formula I, wherein the molecular structural formula is: ; The macrocycle of molecular structure formula I contains 8 benzene rings, and molecular structure formula I includes R, and R is independently selected from hydrogen, substituted or unsubstituted C1~C 30 Alkyl, substituted or unsubstituted C1~C 30 Heteroatoms (one of N, S, O, P, Se, Si, B) alkyl, substituted or unsubstituted C1~C 30 One of the aromatic alkyl groups; n in the molecular structure formula can take an integer value of 0 to 2.

[0019] A method for preparing a type of macrocyclic cyclic molecule modified with carboxylic acid esters, the method comprising the following steps; Preparation of intermediate 1: Under the protection of inert gas, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI, and Et3N and THF solvent system are subjected to Sonogashira-Hagihara coupling reaction, and after separation and purification, the reaction is carried out in a mixed solvent of potassium carbonate, methanol and THF (under the protection of inert gas) to obtain intermediate 1; Preparation of intermediate 2: Under the protection of inert gas, 2,5-dibromo-1,4-diiodobenzene, intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene were subjected to Sonogashira-Hagihara coupling reaction, and intermediate 2 was obtained after separation and purification. Intermediate 2 is one of intermediates V; the relevant characterization of intermediate 2 is as follows Figure 2 As shown (abscissa unit: chemical shift); Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, THF and H2O are subjected to Suzuki-Miyaura coupling reaction; after separation and purification, they are placed in a mixture of HCl, SnCl2·2H2O, and the reaction temperature is low temperature, and dry THF, and after separation and purification, molecular structure I is obtained; the synthesis route is as follows: .

[0020] It needs to be further supplemented that intermediate 2 is one of intermediates V, and the molecular structure of intermediate V is:

[0021] Here, for example, when n is 0, 1, and 2, the synthesis method of intermediate V is as follows: n=0; ; n=1; ; n=2; ;

[0022] The following synthesis method is not the only synthesis method, but is intended to provide a reasonable synthesis route, the goal of which is to protect its structural formula V.

[0023] Here, we only illustrate the synthesis method of intermediate 2 when n is 1 and R is methyl; the synthesis steps are as follows: Synthesis of Methyl-4-ethynylbenzoate: Methyl p-iodobenzoate 1 (4.75 g, 18.13 mmol), trimethylethynylsilane (3.82 mL, 27.20 mmol, TMSA), Pd(PPh3)2Cl2 (400 mg, 0.114 mmol), and CuI (140 mg, 0.74 mmol) were placed in a round-bottom flask (250 mL) containing a solvent system of Et3N (12.5 mL) and THF (50 mL) in an inert argon atmosphere and stirred at room temperature for 24 h. The solvent was removed under reduced pressure, and the mixture was extracted with water (100 mL) and dichloromethane (3×50 mL). The crude products were combined and washed with brine (3×30 mL) and then dried over anhydrous MgSO4; the reaction solution was decompressed to remove dichloromethane, and the crude product was separated and purified by flash column chromatography (petroleum ether: dichloromethane 3:1), and then recrystallized from hexane to obtain a white solid intermediate 4-trimethylsilylethynylbenzoic acid methyl ester (4.13 g, 98%); The intermediate methyl 4-trimethylsilylethynylbenzoate (2.50 g, 10.76 mmol) and potassium carbonate (3.00 g, 21.71 mmol) were dissolved in a round-bottom flask (100 mL) filled with a mixed solvent of methanol (30 mL) and THF (30 mL) (protected by inert gas), and the reaction solution was stirred at room temperature overnight; the reaction solution was evaporated under reduced pressure to remove the solvent, and extracted with 100 mL of water and 3×50 mL of dichloromethane; the crude products were combined, washed with 3×30 mL of brine, and then dried over anhydrous MgSO4; dichloromethane was removed under reduced pressure, and the crude product residue was separated and purified by column chromatography (eluent hexane / dichloromethane: 10:1) to obtain a white powder, intermediate 1 (1.71 g, 99%); 1 H NMR (CDCl3, 400 MHz): δ (ppm) 7.99 (d, J = 8.2 Hz, 2H), 7.54 (d, J =8.2 Hz, 2H), 3.92 (s, 3H), 3.23 (s, 1H).

[0024] Synthesis of 2,5-Dibromo-1,4-diiodobenzene: Place p-dibromobenzene (12.50 g, 53.45 mmol) in a dry round-bottom flask (500 mL) filled with concentrated sulfuric acid (160 mL), and add iodine (51.80 g, 204.10 mmol) in batches; seal the flask under negative pressure, heat to 125-135 °C, and stir to react for 2 days; after cooling to room temperature, pour the mixture into ice water to quench; filter the solid precipitate, and wash it repeatedly with saturated sodium bisulfite solution and sodium bicarbonate solution respectively; the crude product is separated by flash column chromatography (CH2Cl2) to obtain a white compound 2,5-dibromo-1,4-diiodobenzene (20.46 g, 78%), or recrystallize from hot benzene solution; 1 H NMR (CDCl3, 400 MHz): δ (ppm) 8.05 (s, 2 H).

[0025] Synthesis of dimethyl 4,4'-((2,5-dibromo-1,4-phenylene) bis(ethyne-2,1-diyl)) dibenzoate; 2,5-Dibromo-1,4-diiodobenzene (4.4 g, 9.02 mmol), intermediate 1 (3.10 g, 19.35 mmol), diisopropylamine (15 mL) and toluene (45 mL) were added to a round-bottom flask (100 mL) and purged with argon for 15 minutes. Pd(PPh3)2Cl2 (316 mg, 0.45 mmol) and CuI (172 mg, 0.90 mmol) were added and the mixture was purged with argon for 15 minutes again. The reaction was stirred at room temperature for 12 hours. The product was collected by vacuum filtration and washed with Hexane and CH3OH solvents until it was colorless. The product was then placed in a small amount of dichloromethane and stirred, and dried by vacuum filtration to obtain intermediate 2 (4.03 g, 81%). 1 H NMR (CDCl3, 400 MHz): δ (ppm) 8.04 (d, J = 8.7 Hz, 4H), 7.87 (s, 2H), 7.61 (d, J = 8.6 Hz, 4H), 3.94 (s, 6H).

[0026] The above is the preparation method of intermediate 2. Example 2

[0027] In the present invention, the molecular structure II is prepared: intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF and H2O are subjected to Suzuki-Miyaura coupling reaction; after separation and purification, they are placed in a mixture of HCl, SnCl2·2H2O, and can be reacted from an ice water bath to room temperature, dry THF, and after separation and purification, the molecular structure II is obtained; the synthesis route is as follows: ;

[0028] Synthesis of DP

[10] CPP: The bent molecular structure II (180.85 mg, 0.19 mmol), intermediate 2 (102.66 mg, 0.19 mmol), K2CO3 (155 mg, 1.12 mmol), THF (250 mL) and H2O (10 ml) were added to a round-bottom flask (500 mL); argon was passed for 15 minutes, Pd(PPh3)4 (35 mg, 0.03 mmol) was added, and the mixture was passed with argon for 15 minutes again. The reaction was stirred in an oil bath for two or three days; cooled to room temperature, THF in the reaction was removed by decompression, and extracted with H2O (50 mL) and dichloromethane (3×50 mL); the extract was washed with brine (3×30 mL), and the water in the extract was removed with anhydrous MgSO4; after the remaining reaction solution was collected, dichloromethane was removed by decompression, and the residue was dried for the next reaction. The crude product was not further purified; In an argon atmosphere, HCl (0.23 mL, 12 mol / L) was added to a mixture of SnCl2·2H2O (314.61 mg, 1.39 mmol) and dry THF (45 mL), and stirred at room temperature for a period of time; then the resulting solution was dropped into the crude product under inert gas protection with a syringe, and stirred in an ice-water bath for a period of time; after the reaction, the acid in the system was neutralized with an alkaline solution, THF was removed by decompression, and extracted with water (50 mL) and dichloromethane (3×50 mL). The crude product was washed with brine (3×30 mL) and then dried with anhydrous MgSO4; the crude product was purified on a silica gel column with an eluent (hexane / dichloromethane) to obtain a yellow solid compound DP

[10] CPP (26 mg, 22%); especially this reaction was carried out in an ice-water bath; 1 H NMR (CDCl3, 400 MHz): δ (ppm) 8.05 (d, J = 8.3 Hz, 4H), 7.67 (d, J = 8.3 Hz, 4H), 7.55-7.42 (m, 38H), 3.97 (s, 6H).

[0029] The synthesis method of DP[8]CPP is the same as that of DP

[10] CPP, and the molar ratio of the added raw materials is the same; NMR (CDCl3, 400 MHz): δ (ppm) 8.05 (d, J = 8.2 Hz, 4H), 7.66 (d, J= 8.1 Hz, 4H), 7.54-7.43 (m, 30H), 3.97 (s, 6H); Comparison of the synthetic routes of DP[8]CPP and DP

[10] CPP:

[0030] .

[0031] The relevant characteristics of DP

[10] CPP are as follows Figure 1 As shown (abscissa unit: chemical shift); wherein the three-dimensional structural diagrams of molecular formula I and molecular formula II are as shown Fig.18 As shown; The following table lists the photophysical properties of a class of organic light-emitting materials DP[8]CPP and DP

[10] CPP of the present invention, where R is methyl; in tetrahydrofuran (THF), their UV-Vis absorption wavelengths are 327 nm and 330 nm, respectively, their fluorescence wavelengths are 548 nm and 496 nm, and their electroluminescence wavelengths are 562 nm and 527 nm, respectively. After the functional groups are modified, the fluorescence quantum efficiency of DP[8]CPP is increased to 0.42, 3.2 times higher than that of [8]CPP (Φf=0.1); while the photoluminescence quantum efficiency of DP

[10] CPP is increased to 0.77 (

[10] CPP, Φ f =0.46), indicating that this material has good photoelectric properties.

[0032] The following table is a comparison table of the photophysical properties of materials based on molecular formula and molecular structure.

[0033] In the present invention, an electronic device is provided based on the photophysical properties of the materials of molecular structural formula I and molecular structural formula II; the electronic device includes an anode, a cathode and an organic thin film layer arranged between the anode and the cathode, and the material of the organic thin film layer includes the above-mentioned organic compound; the material of the organic thin film layer can be one of the above-mentioned organic compounds, and can also include a mixture of two or more of the above-mentioned organic compounds.

[0034] The preparation method of the electronic device of the present invention comprises the following steps: cleaning 20 mm×20 mm ITO in ethanol and acetone solvents respectively, and drying the ITO in an inert atmosphere for standby use; depositing SnO2 on the ITO; dissolving the product (luminescent layer) and performing spin coating, and annealing the luminescent layer to remove the solvent; vacuum depositing TBPi, Liq, and Al on the film respectively to prepare an OLED device; and finally obtaining an LED luminescent effective area of ​​2×2 mm 2 Its electronic devices such as Figure 3 and Figure 4 As shown; In the present invention, the organic electronic device is as follows: include: First electrode (ITO); An electron transport layer (SnO2, tin dioxide), the organic light-emitting functional layer is on the first electrode; An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP) on the electron transport layer; A hole blocking layer (TBPi, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) on the organic light-emitting functional layer; Electron transport layer (Liq, 8-hydroxyquinoline lithium) on the hole blocking layer; a second electrode, the second electrode being on the electron transport layer; The organic light-emitting functional layer comprises a light-emitting layer; the light-emitting layer comprises the above organic photoelectric compound.

[0035] like Fig. 9 , Fig.10 , Fig.11 and Fig.12 As shown, the J1 / 2-V curves of DP[8]CPP and DP

[10] CPP gave the electron ( μ e ) mobility is 2.29×10 -8 cm 2 ·V -1 ·s -1 and 5.42×10 -5 cm 2 ·V -1 ·s -1 .

[0036] In the present invention, based on the photophysical properties of the materials of molecular structural formula I and molecular structural formula II, a hole device is provided, wherein the hole device comprises an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode, wherein the material of the organic thin film layer comprises the above-mentioned organic compound; the material of the organic thin film layer may be one of the above-mentioned organic compounds, or may comprise a mixture of two or more of the above-mentioned organic compounds; The preparation method of the hollow hole device device of the present invention comprises the following steps: cleaning 20 mm×20 mm ITO in ethanol and acetone solvents respectively, and drying the ITO in an inert atmosphere for standby use; then spin coating the Pedot:PSS layer and the PVK layer on the ITO, and then heating and annealing are performed respectively after completion; the product (luminescent layer) is dissolved and spin coated, and the luminescent layer is also annealed to remove the solvent; MoO3 and Ag are vacuum deposited on the film respectively to prepare a hollow hole device; finally, an LED with an effective luminescent area of ​​2×2 mm is obtained. 2 ; Its hole device device is as follows Figure 5 and Figure 6 As shown; In the present invention, the organic hole device is as follows: First electrode (ITO); A hole injection layer (PEDOT, poly 3,4-ethylenedioxythiophene), which is on top of the first electrode; A hole transport layer (PVK, poly(N-vinylcarbazole)) is located above the hole injection layer; An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP), wherein the organic light-emitting functional layer is on the hole transport layer; Hole transport layer (MoO3, molybdenum trioxide), on the organic light-emitting functional layer; a second electrode, the second electrode being on the hole transport layer; The organic light-emitting functional layer comprises a light-emitting layer; the light-emitting layer comprises the organic photoelectric compound as described above.

[0037] like Fig. 9 , Fig.10 , Fig.11 and Fig.12 As shown, through DP[8]CPP and DP

[10] CPP J 1 / 2 -V curve gets the electron ( μ h ) mobility is 5.85×10 -8 cm 2 ·V -1 ·s -1 and 6.36×10 -7 cm 2 ·V -1 ·s -1 . It shows that DP[8]CPP is suitable as a hole transport material, while DP

[10] CPP is suitable as an electron transport material.

[0038] The present invention also provides an OLED device apparatus, wherein the OLED device comprises an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode, wherein the material of the organic thin film layer comprises the above-mentioned organic compound; the material of the organic thin film layer may be one of the above-mentioned organic compounds, or may comprise a mixture of two or more of the above-mentioned organic compounds; The preparation method of the OLED device in the present invention is to clean 20 mm×20 mm ITO in ethanol and acetone solvents respectively, and place the ITO in an inert atmosphere for drying and standby; then spin-coat the Pedot:PSS layer and PVK layer on the ITO, and after completion, heat and anneal them respectively; spin-coat the product (luminescent layer) solution, and anneal the luminescent layer to remove the solvent; vacuum-deposit TBPi, Liq, and Al on the film respectively to prepare an OLED device. The final LED luminous effective area is 2×2 mm 2 ; Its OLED device device is as follows Figure 7 and Figure 8 As shown; OLED device and energy level diagram based on DP[8]CPP / DP

[10] CPP molecules are shown in Fig.13 As shown; In the present invention, the OLED device is as follows: First electrode (ITO); A hole injection layer (PEDOT:PSS, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)), which is on the first electrode; A hole transport layer (PVK, poly(N-vinylcarbazole)) is located above the hole injection layer; An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP), wherein the organic light-emitting functional layer is on the hole transport layer; A hole blocking layer (TBPi, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) on the organic light-emitting functional layer; a second electrode, the second electrode being on the hole transport layer; The organic light-emitting functional layer comprises a light-emitting layer; the light-emitting layer comprises an organic photoelectric compound.

[0039] like Fig.14 As shown in , Figure a (photographed under ultraviolet light) and Figure b (photographed under normal light) are actual pictures of DP[8]CPP as an OLED device; Figure c (photographed under ultraviolet light) and Figure d (photographed under normal light) are actual pictures of DP

[10] CPP as an OLED device; like Fig.15 , Fig.16 and Fig.17As shown in the figure, the device threshold voltages of OLEDs of DP[8]CPP and DP

[10] CPP are 7.55 eV and 2.90 eV, respectively. 3 cd / m 2 When , the voltages are 13.22 V and 6.90 V respectively, and the withstand voltage of DP[8]CPP is twice that of DP

[10] CPP.

[0040] Compared with the traditional linear aromatic conjugated structure, the skeleton of the cyclic π-conjugated compound has a stronger electron transfer ability; by connecting different groups, such as R groups, to the cyclic skeleton, the electronic properties of the molecule can be adjusted to have a bipolar structure, which is conducive to the transmission and recombination of electrons and holes; introducing specific groups into the macrocycle increases the electron transfer channel, thereby improving the luminescence efficiency of devices containing such molecules; At the same time, this structure can also reduce the intermolecular forces and reduce the π-π stacking between molecules. The introduction of flexible functional groups further improves the solubility of the molecules, enhances the solubility of the luminescent functional film, and reduces defects within the film.

[0041] In terms of devices, taking electronic devices as an example, ITO is used as the anode, and SnO2 is first deposited on it to form an electron transport layer; this layer helps to effectively transport electrons from the cathode to the light-emitting layer; then, a light-emitting layer containing a new macrocyclic molecule is spin-coated, which is the core area of ​​electron and hole recombination luminescence; then the hole blocking layer TBPi and the electron transport layer Liq are deposited in sequence. The hole blocking layer can effectively prevent excessive hole transmission and ensure that electrons and holes recombine more effectively in the light-emitting layer; finally, the cathode Al is deposited to complete the entire device structure; during operation, electrons are injected from the cathode, pass through the electron transport layer, and meet and recombine with holes injected from the anode and transmitted through the hole transport layer in the light-emitting layer, thereby generating light; due to the different electron mobilities of DP[8]CPP and DP

[10] CPP, their performance in electronic devices is different.

[0042] For hole devices, ITO is also used as the anode, and PEDOT:PSS is spin-coated as a hole injection layer and PVK as a hole transport layer. These two layers help to efficiently inject and transport holes from the anode. The light-emitting layer is then spin-coated, and the hole transport layer MoO3 and cathode Ag are deposited in sequence. During operation, holes are injected from the anode, pass through the hole injection layer and the transport layer to reach the light-emitting layer, and recombine with electrons to emit light. The different hole mobilities of DP[8]CPP and DP

[10] CPP make them different in applicability in hole devices. For example, DP[8]CPP is more suitable as a hole transport material, while DP

[10] CPP is more suitable as an electron transport material.

[0043] In OLED devices, ITO is used as the anode, and PEDOT:PSS is spin-coated as the hole injection layer, PVK is spin-coated as the hole transport layer, and then the light-emitting layer is spin-coated, and then the hole blocking layer TBPi is deposited, and finally the cathode is deposited; during operation, holes and electrons are injected from the anode and cathode respectively, and efficiently recombine in the light-emitting layer to achieve light emission; DP[8]CPP and DP

[10] CPP have different turn-on voltages and withstand different voltages at maximum brightness, which reflects their performance differences in OLED devices. Different application requirements can be met by selecting appropriate materials.

[0044] Through the design and synthesis of new macrocyclic cyclic molecules and their application in different types of devices, electronic, hole and OLED devices with specific optoelectronic properties have been achieved, providing new solutions and possibilities in the field of organic materials and electroluminescent devices.

[0045] The above-mentioned embodiments only express the implementation methods of the present invention, and cannot be understood as limiting the scope of the invention patent, nor is it any form of limitation on the structure of the present invention. It should be pointed out that for ordinary technicians in this field, several changes and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A macrocyclic molecule modified with a carboxylic acid ester, characterized in that: It includes molecular structural formula I, and the molecular structural formula is: ； The macrocycle of the molecular structural formula I contains 8 benzene rings, and the molecular structural formula I includes R, wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C1~C 30 Heteroatom alkyl, substituted or unsubstituted C1~C 30 One of the aromatic alkyl groups; n in the molecular structure formula can take an integer value of 0 to 2.

2. A method for preparing a macrocyclic molecule of a modified carboxylic acid ester as claimed in claim 1, characterized in that: The method comprises the following steps: Preparation of intermediate 1: Under the protection of inert gas, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI are added to Et3N and tetrahydrofuran (THF) solvent system to carry out Sonogashira-Hagihara coupling reaction, and after separating and purifying the product, it is reacted in a mixed solvent of potassium carbonate, methanol and tetrahydrofuran (THF) under the protection of inert gas to obtain intermediate 1; Preparation of intermediate 2: Under the protection of inert gas, 2,5-dibromo-1,4-diiodobenzene, intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene are subjected to Sonogashira-Hagihara coupling reaction, and intermediate 2 is obtained after separation and purification, and intermediate 2 is one of intermediates V; Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, tetrahydrofuran THF and H2O are subjected to Suzuki-Miyaura coupling reaction; after separation and purification of the product, it is placed in a mixed solvent of HCl and SnCl2·2H2O, the reaction temperature is low temperature, and after separation and purification, the molecular structure I is obtained; the synthesis route is as follows: 。 3. The method for preparing a macrocyclic cyclic molecule of a modified carboxylic acid ester according to claim 2, characterized in that: The Sonogashira-Hagihara coupling reaction is carried out in an Et3N and tetrahydrofuran THF solvent system, and then the aromatization reaction is carried out in HCl, SnCl2·2H2O at low temperature.

4. The method for preparing a macrocyclic cyclic molecule of a modified carboxylic acid ester according to claim 2, characterized in that: Intermediate 2 is a type of intermediate V, and its molecular structure is: ; n is 0, 1, or 2 respectively.

5. The method for preparing a macrocyclic cyclic molecule of a modified carboxylic acid ester according to claim 4, characterized in that: Intermediate 2 is one of Intermediate V. When n is 1 and R is methyl, the synthesis steps of Intermediate 2 are as follows; Preparation of 2,5-dibromo-1,4-diiodobenzene: place p-dibromobenzene in a dry round-bottom flask filled with concentrated sulfuric acid, add iodine in batches; seal the flask under negative pressure, heat to 125-135°C, and stir to react for 2 days; after cooling to room temperature, pour the mixture into ice water to quench; filter the obtained solid precipitate, and wash it repeatedly with saturated sodium bisulfite solution and sodium bicarbonate solution respectively; the obtained crude product is separated by flash column chromatography to obtain a white compound 2,5-dibromo-1,4-diiodobenzene, or recrystallized in hot benzene solution; Preparation of dimethyl 4,4'-((2,5-dibromo-1,4-phenylene)bis(acetylene-2,1-diyl))dibenzoate: 2,5-dibromo-1,4-diiodobenzene, intermediate 1, diisopropylamine and toluene were added to a round-bottom flask and purged with argon for 15 minutes, then Pd(PPh3)2Cl2 and CuI were added, and the mixture was purged with argon for 15 minutes again; the reaction was stirred at room temperature for 12 hours; the product was collected by vacuum filtration, and washed with Hexane and CH3OH solvents until it was colorless; the product was then placed in a small amount of dichloromethane and stirred, and dried by vacuum filtration to obtain intermediate 2. The synthetic route is as follows: 。 6. A macrocyclic molecule modified with a carboxylic acid ester, characterized in that: It includes molecular structural formula II, and the molecular structure is: ； The macrocycle of the molecular structural formula II contains 10 benzene rings; the molecular structural formula II includes R, wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C1~C 30 Heteroatom alkyl, substituted or unsubstituted C1~C 30 One of the aromatic alkyl groups; n in the molecular structure formula can take an integer value of 0 to 2.

7. The method for preparing a macrocyclic cyclic molecule of a modified carboxylic acid ester according to claim 6, characterized in that: The steps for preparing intermediate 1 and intermediate 2 are the same as those for preparing the molecular structure I; Preparation of molecular structure II: Intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF and H2O are subjected to Suzuki-Miyaura coupling reaction; after separation and purification, they are placed in a mixture of HCl, SnCl2·2H2O, and can be reacted from an ice water bath to room temperature, and dried tetrahydrofuran THF, and molecular structure II is obtained after separation and purification; the synthetic route is as follows: 。 8. An application of a macrocyclic molecule modified with a carboxylic acid ester as claimed in claim 1 or claim 6, characterized in that: The macrocyclic molecule is used for making light-emitting devices, which include electronic devices, hole devices and OLED devices, and the electronic devices, hole devices and OLED devices all include functional thin film layers.

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