Modified carboxylate macrocyclic ring molecules, methods of making and using the same

Abstract

The application discloses a kind of modified carboxylate macrocyclic molecules and preparation method and application thereof, it is related to organic material and electroluminescent device technical field;Macrocyclic molecules include molecular structure formula I and molecular structure formula II, and the macrocycle of it respectively contains 8 and 10 1,4-para phenylene, R in structure can be selected variously;Its synthesis method includes the steps of gradually connecting carboxylate monomer, using template to guide ring formation, intramolecular ring closure reaction and palladium catalysis reaction;Device based on this molecule has electronic device, hole device and OLED device, all contain functional film layer, and preparation method is various;The molecule and device of the application have outstanding photoelectric performance, can reduce intermolecular force, reduce π-π stacking, improve solubility, reduce device start-up voltage, control luminescent color;Through application in different devices, provide a new solution for related field, with wide application prospect.

Description

Technical Field

[0001] This invention relates to the fields of organic materials and electroluminescent devices, specifically to a class of macrocyclic molecules modified with carboxylic acid esters, their preparation methods, and applications. Background Technology

[0002] OLEDs are diodes that emit light when an electric current is passed through them. The device structures are either active or passive; active OLEDs use thin-film transistors to control the current. Unlike traditional LCDs, they do not require a backlight and offer advantages such as thinner profiles, lighter weight, higher contrast, faster response times, wider viewing angles, and lower power consumption, making them 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), an emissive layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL). An organic light-emitting material layer is sandwiched between the anode and cathode. After charge is injected into the organic light-emitting material, electron-hole recombination occurs, generating light. OLEDs are simple to manufacture, requiring only low-voltage driving, giving them a significant advantage in flat panel display applications. In recent years, the performance of OLED devices has been significantly improved by controlling the molecular structure of materials, optimizing device structure and processes, and introducing new materials and technologies. In particular, the introduction of new materials has met new consumer demands for display technology, driving the development and application of OLED technology. The key to optimizing OLED devices lies in improving the luminous efficiency of materials, charge injection balance and stability, and reducing device power consumption, thereby continuously improving their performance in various display devices.

[0004] The photophysical properties of the end-to-end cyclic biphenyl structure are superior to those of the linear biphenyl structure commonly used in OLEDs, exhibiting properties similar to carbon nanotubes. It displays even more prominent photophysical properties in solution, thin film, and crystalline forms, and the cyclic structure and π-conjugated system have attracted increasing interest in the field of organic semiconductors. Theoretical methods predict that a series of carbon nanorings and their derivatives possess high electron mobility, showing great potential in electroluminescent materials; therefore, this invention proposes a class of macrocyclic molecules modified with carboxylic acid esters, their preparation methods, and applications. Summary of the Invention

[0005] The purpose of this invention is to provide a class of macrocyclic organic materials containing carboxylic acid esters, which can be used in light-emitting devices or electroluminescent devices, particularly organic light-emitting diodes (OLEDs); said devices include a light-emitting layer and at least two electrodes; the invention also relates to apparatuses comprising said electronic devices, hole devices and / or OLEDs, to solve the problems raised in the background above.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a class of macrocyclic molecules modified with carboxylic acid esters, comprising molecular structural formula I, wherein the molecular structural formula is:

[0007] ;

[0008] Furthermore, the macrocycle of molecular structure I contains eight benzene rings, and molecular structure I includes R, wherein R is independently selected from hydrogen, substituted or unsubstituted C1 to C2. 30 Alkyl, substituted or unsubstituted C1-C 30 Heteroatoms (one of N, S, O, P, Se, Si, B), alkyl groups, substituted or unsubstituted C1-C2 atoms. 30 One of the aromatic alkyl groups; n in the molecular structural formula can take integer values ​​from 0 to 2.

[0009] Furthermore, a class of macrocyclic molecules modified with carboxylic acid esters also includes those with molecular structure formula II, the molecular structure of which is:

[0010] ;

[0011] A method for preparing a class of macrocyclic molecules modified carboxylic acid esters, the method comprising the following steps;

[0012] Preparation of intermediate 1: Under inert gas protection, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI, and Et3N and THF solvent system were subjected to Sonogashira-Hagihara coupling reaction. After separation and purification, intermediate 1 was obtained by reaction in a mixed solvent of potassium carbonate, methanol and THF (under inert gas protection).

[0013] Preparation of intermediate 2: Under inert gas protection, 2,5-dibromo-1,4-diiodobenzene, intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene were subjected to a Sonogashira-Hagihara coupling reaction. After separation and purification, intermediate 2 was obtained. Intermediate 2 is one of intermediates V.

[0014] Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, THF, and H2O were coupled via a Suzuki-Miyaura reaction. After separation and purification, the mixture was placed in a low-temperature mixture of HCl, SnCl2·2H2O, and dry THF. After further separation and purification, molecular structure I was obtained. The synthetic route is shown below:

[0015] Furthermore, the Sonogashira-Hagihara coupling reaction was carried out in a solvent system of Et3N (12.5 mL) and THF (50 mL).

[0016] Furthermore, intermediate 2 is a type of intermediate V, with the following molecular structural formula:

[0017] ;

[0018] n can be 0, 1, or 2.

[0019] When n is 1 and R is methyl, the synthesis steps of intermediate 2 are as follows;

[0020] Preparation of 2,5-dibromo-1,4-diiodobenzene: p-Dibromobenzene (12.50 g, 53.45 mmol) was placed in a dry round-bottom flask (500 mL) containing concentrated sulfuric acid (160 mL), and iodine (51.80 g, 204.10 mmol) was added in portions; the flask was sealed under negative pressure, heated to 125-135 °C, and stirred for 2 days; after cooling to room temperature, the mixture was poured into ice water for quenching; the resulting solid precipitate was repeatedly washed with saturated sodium bisulfite solution and sodium bicarbonate solution, respectively; the crude product was separated by rapid column chromatography (CH2Cl2) to obtain the white compound 2,5-dibromo-1,4-diiodobenzene (20.46 g, 78%), or recrystallized in hot benzene solution;

[0021] Preparation of 4,4'-((2,5-dibromo-1,4-phenylene)bis(acetylene-2,1-diyl))dimethyl benzoate: 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). After purging 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 again for 15 minutes. 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 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 shown below: ;

[0022] Further, in preparing molecular structure II: intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF, and H2O were coupled via a Suzuki-Miyaura coupling reaction; after separation and purification, they were placed in a mixture of HCl, SnCl2·2H2O, and reacted at room temperature in an ice-water bath. After separation and purification, molecular structure II was obtained. The synthetic route is shown below:

[0023]

[0024] An application of a macrocyclic molecule modified with a carboxylic acid ester as described above, wherein the macrocyclic molecule is used to fabricate a light-emitting device, the light-emitting device including an electronic device, a hole device, and an OLED device, wherein the electronic device, hole device, and OLED device all include a functional thin film layer.

[0025] The beneficial effects of this invention are as follows:

[0026] (1) In the technical solution of this application, compared with linear aromatic conjugation, the skeleton of organic cyclic π-conjugated compounds has a strong electron transfer capability and more outstanding photoelectric performance. Moreover, the cyclic skeleton is connected with groups with electron capabilities, so that the compound has a bipolar structure, which is conducive to the transport and recombination of electrons and holes. The introduction of groups into the macrocycle increases the electron transfer channels of the macrocycle, which can improve the luminous efficiency of the device containing it; at the same time, this structure can reduce the intermolecular forces and reduce the π-π stacking between molecules; the introduction of flexible functional groups can improve the solubility of molecules, improve the solubility of the luminescent functional film, and reduce defects in the film; carbon nanorings are ultrashort structures of carbon nanotubes and have the performance 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 regulate the luminous color of the OLED device.

[0027] (2) The present invention obtained macrocyclic compounds of methyl carboxylate through molecular design; the macrocyclic compounds of methyl carboxylate provided by the present invention DP

[10] CPP can be used as electron transport materials for OLED light-emitting devices, and DP[8]CPP can be used as hole transport materials for OLED light-emitting devices. Attached Figure Description

[0028] Figure 1 For DP

[10] CPP 1 H NMR spectrum;

[0029] Figure 2 For intermediate 2 1 H NMR plot;

[0030] Figure 3Schematic diagram of electronic device structure Figure 1 ;

[0031] Figure 4 Schematic diagram of electronic device structure Figure 2 ;

[0032] Figure 5 Schematic diagram of hole device structure Figure 1 ;

[0033] Figure 6 Schematic diagram of hole device structure Figure 2 ;

[0034] Figure 7 Schematic diagram of OLED device structure Figure 1 ;

[0035] Figure 8 Schematic diagram of OLED device structure Figure 2 ;

[0036] Figure 9 For DP[8]CPP electronic devices J 1 / 2 - V and fitted curve plot;

[0037] Figure 10 For DP[8]CPP hole devices J 1 / 2 - V and fitted curve plot;

[0038] Figure 11 For electronic devices of DP

[10] CPP J 1 / 2 - V and fitted curve plot;

[0039] Figure 12 Hole devices for DP

[10] CPP J 1 / 2 - V and fitted curve plot;

[0040] Figure 13 A schematic diagram of OLED devices and energy levels based on DP[8]CPP / DP

[10] CPP molecules;

[0041] Figure 14 Physical diagrams of the OLED device structures of DP[8]CPP and DP

[10] CPP;

[0042] Figure 15 The curves of current density versus voltage for DP[8]CPP and DP

[10] CPP are shown.

[0043] Figure 16 The curves of brightness versus voltage for DP[8]CPP and DP

[10] CPP are shown.

[0044] Figure 17 The external fluorescence quantum efficiency versus voltage curves for DP[8]CPP and DP

[10] CPP are shown.

[0045] Figure 18 These are schematic diagrams of the three-dimensional structures of molecular structural formula I and molecular structural formula II; Detailed Implementation

[0046] To make the inventive objectives, technical solutions, and beneficial technical effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the embodiments described in this specification are merely illustrative and not intended to limit the scope of the application. The following examples are provided for the purpose of more detailed description of the invention, but are not exhaustive and are intended to be representative.

[0047] In this invention, terms such as "cyclic" and "macrocyclic" refer to an Armchair-type macrocyclic structure composed of multiple para-phenylene groups; "a," "a class," and "the" all refer to one or more molecules of the compound, and are not limited to a single molecule of the compound. Example 1

[0048] A class of macrocyclic molecules modified with carboxylic acid esters, including molecular structure I, with the following molecular structure:

[0049] ;

[0050] Molecular structural formula I contains eight benzene rings in its macrocycle. Molecular structural formula I includes R, where R is independently selected from hydrogen, substituted or unsubstituted C1 to C2. 30 Alkyl, substituted or unsubstituted C1-C 30 Heteroatoms (one of N, S, O, P, Se, Si, B), alkyl groups, substituted or unsubstituted C1-C2 atoms. 30 One of the aromatic alkyl groups; n in the molecular structural formula can take integer values ​​from 0 to 2.

[0051] A method for preparing a class of macrocyclic molecules modified carboxylic acid esters, the method comprising the following steps;

[0052] Preparation of intermediate 1: Under inert gas protection, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI, and Et3N and THF solvent system were subjected to Sonogashira-Hagihara coupling reaction. After separation and purification, intermediate 1 was obtained by reaction in a mixed solvent of potassium carbonate, methanol and THF (under inert gas protection).

[0053] Preparation of Intermediate 2: Under inert gas protection, 2,5-dibromo-1,4-diiodobenzene, Intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene were subjected to a Sonogashira-Hagihara coupling reaction. After separation and purification, Intermediate 2 was obtained, which is one of Intermediates V. The relevant characterization of Intermediate 2 is as follows: Figure 2 As shown (horizontal axis unit: chemical shift);

[0054] Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, THF, and H2O were coupled via a Suzuki-Miyaura reaction. After separation and purification, the mixture was placed in a low-temperature mixture of HCl, SnCl2·2H2O, and dry THF to obtain molecular structure I. The synthetic route is shown below: .

[0055] Further information is needed: Intermediate 2 is one of intermediates V, and the molecular structural formula of intermediate V is as follows:

[0056]

[0057] This is just one example illustrating the synthesis method of intermediate V when n takes the values ​​of 0, 1, and 2. The route is as follows:

[0058] n=0;

[0059] ;

[0060] n=1;

[0061] ;

[0062] n=2;

[0063] ;

[0064] The following synthesis method is not the only synthesis method, but is intended to provide a reasonable synthesis path with the goal of protecting its structural formula V.

[0065] This example illustrates the synthesis method of intermediate 2 when n is 1 and R is a methyl group; the synthesis steps are as follows.

[0066] Synthesis of methyl-4-ethynylbenzoate:

[0067] 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 Et3N (12.5 mL) and THF (50 mL) under 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 extracted with brine (3 × 30 mL). Wash with mL and dry with anhydrous MgSO4; remove dichloromethane from the reaction solution under reduced pressure, separate and purify the crude product by rapid column chromatography (petroleum ether: dichloromethane = 3:1), and then recrystallize with hexane to obtain a white solid intermediate methyl 4-trimethylsilylethynylbenzoate (4.13 g, 98%).

[0068] 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) containing a mixture of methanol (30 mL) and THF (30 mL) under inert gas protection. The reaction mixture was stirred overnight at room temperature. The solvent was removed by rotary evaporation under reduced pressure, and the mixture was 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 dried over anhydrous MgSO4. Dichloromethane was removed under reduced pressure, and the crude product residue was purified by column chromatography (eluent: hexane / dichloromethane: 10:1) to give a white powder, intermediate 1 (1.71 g, 99%).

[0069] 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).

[0070] Synthesis of 2,5-dibromo-1,4-diiodobenzene:

[0071] p-Dibromobenzene (12.50 g, 53.45 mmol) was placed in a dry round-bottom flask (500 mL) containing concentrated sulfuric acid (160 mL), and iodine (51.80 g, 204.10 mmol) was added in portions. The flask was sealed under negative pressure, heated to 125-135 °C, and stirred for 2 days. After cooling to room temperature, the mixture was poured into ice water to quench it. The resulting solid precipitate was repeatedly washed with saturated sodium bisulfite solution and sodium bicarbonate solution, respectively. The crude product was separated by rapid column chromatography (CH2Cl2) to obtain the white compound 2,5-dibromo-1,4-diiodobenzene (20.46 g, 78%), or recrystallized from hot benzene solution.

[0072] 1 H NMR (CDCl3, 400 MHz): δ (ppm) 8.05 (s, 2 H).

[0073] Synthesis of dimethyl 4,4'-((2,5-dibromo-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzoate;

[0074] 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). Argon gas was purged for 15 minutes, then Pd(PPh3)2Cl2 (316 mg, 0.45 mmol) and CuI (172 mg, 0.90 mmol) were added, and the mixture was purged with argon gas again for 15 minutes. 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 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%).

[0075] 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).

[0076] The above describes the preparation method of intermediate 2. Example 2

[0077] In this invention, molecular structure II is prepared by: intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF, and H2O via a Suzuki-Miyaura coupling reaction; after separation and purification, it is placed in a mixture of HCl, SnCl2·2H2O, and the reaction can be carried out from an ice-water bath to room temperature, and dry THF. After separation and purification, molecular structure II is obtained. The synthetic route is shown below:

[0078] ;

[0079] Synthesis of DP

[10] CPP:

[0080] Curved 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 gas was purged for 15 minutes, and Pd(PPh3)4 (35 mg, 0.03 mmol) was added. The mixture was purged with argon gas again for 15 minutes, and the reaction was stirred in an oil bath for two or three days. After cooling to room temperature, THF was removed from the reaction mixture under reduced pressure, and the mixture was 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. The remaining reaction mixture was collected, and dichloromethane was removed under reduced pressure. The residue was dried for the next reaction. The crude product was not further purified.

[0081] 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. The resulting solution was then added dropwise to the crude product under inert gas protection using 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 vacuum, and the mixture was extracted with water (50 mL) and dichloromethane (3 × 50 mL). The crude product was washed with brine (3 × 30 mL) and dried with anhydrous MgSO4. The crude product was purified on a silica gel column with an eluent (hexane / dichloromethane) to give a yellow solid compound DP

[10] CPP (26 mg, 22%). This reaction was especially carried out in an ice-water bath.

[0082] 1H 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).

[0083] 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);

[0084] Comparison of synthetic routes of DP[8]CPP and DP

[10] CPP:

[0085]

[0086] .

[0087] The relevant characterizations of DP

[10] CPP are as follows Figure 1 As shown (horizontal axis unit: chemical shift); the stereoscopic structural diagrams of molecular structural formula I and molecular structural formula II are shown below. Figure 18 As shown;

[0088] The following table lists the photophysical properties of DP[8]CPP and DP

[10] CPP, two organic light-emitting materials 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 modifying the functional groups, compared with [8]CPP (Φf=0.1), the fluorescence quantum efficiency of DP[8]CPP increased to 0.42, which is 3.2 times higher; while the photoluminescence quantum efficiency of DP

[10] CPP increased to 0.77 (

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

[0089] The table below is a comparison table of photophysical properties of materials based on molecular structural formulas and molecular structural formulas.

[0090]

[0091] In this invention, based on the photophysical properties of materials with molecular structural formulas I and II, an electronic device is provided; the electronic device includes 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 includes the aforementioned organic compounds; the material of the organic thin film layer may be one of the aforementioned organic compounds, or may include a mixture of two or more of the aforementioned organic compounds.

[0092] The electronic device fabrication method of this invention involves cleaning a 20 mm × 20 mm ITO layer with ethanol and acetone solvents, and then drying the ITO layer under an inert atmosphere for later use. SnO2 is then deposited on the ITO layer. The product (light-emitting layer) is dissolved and spin-coated, and the light-emitting layer is annealed to remove the solvent. TBPi, Liq, and Al are then deposited onto the film under vacuum to fabricate an OLED device. Finally, an LED with an effective light-emitting area of ​​2 × 2 mm is obtained. 2 Its electronic devices, such as Figure 3 and Figure 4 As shown;

[0093] In this invention, the organic electronic device is as follows:

[0094] include:

[0095] First electrode (ITO);

[0096] An electron transport layer (SnO2, tin dioxide) is placed on the first electrode;

[0097] An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP) is placed above the electron transport layer;

[0098] Hole blocking layer (TBPi, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) on organic light-emitting functional layer;

[0099] An electron transport layer (Liq, lithium 8-hydroxyquinoline) is placed on a hole-blocking layer.

[0100] The second electrode is located above the electron transport layer;

[0101] The organic light-emitting functional layer includes a light-emitting layer; the light-emitting layer contains the organic photoelectric compounds described above.

[0102] like Figure 9 , Figure 10 , Figure 11 and Figure 12 As shown, the electron ( ) was obtained from the J1 / 2-V curves of DP[8]CPP and DP

[10] CPP. μ eThe mobility rates were 2.29 × 10⁻⁶. -8 cm 2 ·V -1 ·s -1 and 5.42×10 -5 cm 2 ·V -1 ·s -1 .

[0103] In this invention, based on the photophysical properties of materials with molecular structural formulas I and II, a hole device is provided. The hole device includes an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode. The material of the organic thin film layer includes the aforementioned organic compounds. The material of the organic thin film layer can be one of the aforementioned organic compounds, or it can include a mixture of two or more of the aforementioned organic compounds.

[0104] The hole device in this invention is prepared by first cleaning a 20 mm × 20 mm ITO layer with ethanol and acetone solvents, and then drying the ITO under an inert atmosphere. A Pedot:PSS layer and a PVK layer are then spin-coated onto the ITO, followed by annealing. The product (light-emitting layer) is dissolved and spin-coated, and then annealed to remove the solvent. MoO3 and Ag are deposited onto the film under vacuum to prepare the hole device. Finally, an LED with an effective light-emitting area of ​​2 × 2 mm is obtained. 2 Its hole-device device, such as Figure 5 and Figure 6 As shown;

[0105] In this invention, the organic hole device is as follows:

[0106] First electrode (ITO);

[0107] Hole injection layer (PEDOT, poly3,4-ethylenedioxythiophene), which is placed on the first electrode;

[0108] Hole transport layer (PVK, poly(N-vinylcarbazole)), which is above the hole injection layer;

[0109] An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP) is placed on top of the hole transport layer;

[0110] Hole transport layer (MoO3, molybdenum trioxide), on organic light-emitting functional layer;

[0111] The second electrode is located above the hole transport layer;

[0112] The organic light-emitting functional layer includes a light-emitting layer; the light-emitting layer contains the organic photoelectric compound described above.

[0113] like Figure 9 , Figure 10 , Figure 11 and Figure 12 As shown, through DP[8]CPP and DP

[10] CPP J 1 / 2 The -V curve yielded electrons ( μ h The mobility rates were 5.85 × 10⁻⁶. -8 cm 2 ·V -1 ·s -1 and 6.36×10 -7 cm 2 ·V -1 ·s -1 This indicates that DP[8]CPP is suitable as a hole transport material, while DP

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

[0114] The present invention also provides an OLED device, the OLED device including an anode, a cathode and an organic thin film layer disposed between the anode and the cathode, the material of the organic thin film layer including the above-mentioned organic compounds; the material of the organic thin film layer may be one of the above-mentioned organic compounds, or may include a mixture of two or more of the above-mentioned organic compounds;

[0115] The OLED device fabrication method of this invention involves cleaning a 20 mm × 20 mm ITO layer with ethanol and acetone solvents, and then drying the ITO under an inert atmosphere. A Pedot:PSS layer and a PVK layer are then spin-coated onto the ITO, followed by heating and annealing. The product (light-emitting layer) solution is then spin-coated, and the light-emitting layer is also annealed to remove the solvent. Finally, TBPi, Liq, and Al are vacuum-deposited onto the film to fabricate the OLED device. The resulting LED has an effective light-emitting area of ​​2 × 2 mm. 2 Its OLED device devices, such as Figure 7 and Figure 8 As shown; a schematic diagram of OLED devices and energy levels based on DP[8]CPP / DP

[10] CPP molecules is shown below. Figure 13 As shown;

[0116] In this invention, the OLED device is as follows:

[0117] First electrode (ITO);

[0118] Hole injection layer (PEDOT: PSS, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)), which is placed on the first electrode;

[0119] Hole transport layer (PVK, poly(N-vinylcarbazole)), which is above the hole injection layer;

[0120] An organic light-emitting functional layer (DP

[10] CPP or DP[8]CPP) is placed on top of the hole transport layer;

[0121] Hole blocking layer (TBPi, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene) on organic light-emitting functional layer;

[0122] The second electrode is located above the hole transport layer;

[0123] The organic light-emitting functional layer includes a light-emitting layer; the light-emitting layer contains organic photoelectric compounds.

[0124] like Figure 14 As shown in the figure, Figure a (taken under ultraviolet light) and Figure b (taken under normal light) are actual pictures of DP[8]CPP as an OLED device; Figure c (taken under ultraviolet light) and Figure d (taken under normal light) are actual pictures of DP

[10] CPP as an OLED device.

[0125] like Figure 15 , Figure 16 and Figure 17 As shown, the device threshold voltages of DP[8]CPP and DP

[10] CPP OLEDs are 7.55 eV and 2.90 eV, respectively, when the maximum brightness is 10 3 cd / m 2 At that time, their voltages were 13.22 V and 6.90 V respectively, and the withstand voltage of DP[8]CPP was twice that of DP

[10] CPP.

[0126] Compared with traditional linear aromatic conjugated structures, cyclic π-conjugated compounds have stronger electron transfer capabilities. By attaching different groups, such as R groups, to the cyclic backbone, the electronic properties of the molecule can be tuned to give it a bipolar structure, which is beneficial for the transport and recombination of electrons and holes. Introducing specific groups into the macrocycle increases the electron transfer channels, thereby improving the luminescence efficiency of devices containing such molecules.

[0127] At the same time, this structure can reduce intermolecular forces, reduce π-π stacking between molecules, introduce flexible functional groups to further improve the solubility of molecules, enhance the solubility of the luminescent functional film, and reduce defects in the film.

[0128] 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 the electrons to be effectively transported from the cathode to the light-emitting layer. Then, a light-emitting layer containing novel macrocyclic molecules is spin-coated. This light-emitting layer is the core area for electron and hole recombination light emission. After that, a hole blocking layer TBPi and an electron transport layer Liq are deposited in sequence. The hole blocking layer can effectively prevent excessive hole transport 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. When working, electrons are injected from the cathode, pass through the electron transport layer, and meet and recombine with holes injected from the anode and transported through the hole transport layer in the light-emitting layer, thereby generating light emission. Due to the different electron mobility of DP[8]CPP and DP

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

[0129] For hole devices, ITO is used as the anode, and PEDOT:PSS is spin-coated as the hole injection layer and PVK as the hole transport layer in sequence. These two layers help the holes to be injected and transported efficiently from the anode. Then, the light-emitting layer is spin-coated, and then the hole transport layer MoO3 and the 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 hole mobility of DP[8]CPP and DP

[10] CPP is different, which makes them different in their 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.

[0130] In OLED devices, ITO is used as the anode, PEDOT:PSS is spin-coated as the hole injection layer and PVK as the hole transport layer, then the light-emitting layer is spin-coated, 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 they recombine efficiently in the light-emitting layer to achieve light emission. DP[8]CPP and DP

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

[0131] By designing and synthesizing novel macrocyclic molecules and applying them in different types of devices, electronic, hole, and OLED devices with specific optoelectronic properties have been realized, providing new solutions and possibilities for the fields of organic materials and electroluminescent devices.

[0132] The embodiments described above merely illustrate implementation methods of the present invention and should not be construed as limiting the scope of the invention patent, nor as imposing any form of limitation on the structure of the present invention. It should be noted that those skilled in the art can make various changes and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A class of macrocyclic molecules modified with carboxylic acid esters, characterized in that: The macrocyclic molecule has the following molecular structural formula I: ； R is a methyl group; n in molecular formula I is 1.

2. A method for preparing a macrocyclic molecule of a type of modified carboxylic acid ester as described in claim 1, characterized in that: The method includes the following steps; Preparation of intermediate 1: Under inert gas protection, methyl p-iodobenzoate, trimethylethynylsilane, Pd(PPh3)2Cl2 and CuI were added to a solvent system of Et3N and tetrahydrofuran to carry out a Sonogashira-Hagihara coupling reaction. After the product was separated and purified, it was reacted in a mixed solvent of potassium carbonate, methanol and tetrahydrofuran under inert gas protection to obtain intermediate 1. Preparation of intermediate 2: Under inert gas protection, 2,5-dibromo-1,4-diiodobenzene, intermediate 1, Pd(PPh3)2Cl2 and CuI, diisopropylamine and toluene were subjected to a Sonogashira-Hagihara coupling reaction, and intermediate 2 was obtained after separation and purification. Preparation of molecular structure I: Intermediate 2, bent molecular structure I, K2CO3, Pd(PPh3)4, tetrahydrofuran, and H2O were coupled via a Suzuki-Miyaura reaction. After separation and purification of the product, it was placed in a mixed solvent of HCl and SnCl2·2H2O at a low temperature to obtain molecular structure I after further separation and purification. The synthetic route is shown below: ； R is a methyl group; n in molecular formula I is 1.

3. The method for preparing a type of macrocyclic molecule modified carboxylic acid ester according to claim 2, characterized in that, The synthesis steps of intermediate 2 are as follows; Preparation of 2,5-dibromo-1,4-diiodobenzene: p-Dibromobenzene was placed in a dry round-bottom flask containing concentrated sulfuric acid, and iodine was added in batches; the flask was sealed under negative pressure, heated to 125-135 °C, and stirred for 2 days; after cooling to room temperature, the mixture was poured into ice water for quenching; the resulting solid precipitate was repeatedly washed with saturated sodium bisulfite solution and sodium bicarbonate solution, respectively; the crude product was separated by rapid column chromatography to obtain the white compound 2,5-dibromo-1,4-diiodobenzene, or recrystallized from hot benzene solution; Preparation of Intermediate 2: 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 again for 15 minutes. The reaction was stirred at room temperature for 12 hours. The product was collected by vacuum filtration and washed with hexane and CH3OH solvent until 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 shown below: 。 4. A class of macrocyclic molecules modified with carboxylic acid esters, characterized in that: The macrocyclic molecule has the following molecular structural formula II: ； R is a methyl group; n in molecular formula II is 1.

5. The method for preparing a type of modified carboxylic acid ester macrocyclic molecule according to claim 4, characterized in that, The steps for preparing intermediate 1 and intermediate 2 are the same as those for preparing intermediate 1 and intermediate 2 in the method for preparing a type of modified carboxylic acid ester macrocyclic molecule as described in any one of claims 2-3. Preparation of molecular structure II: Intermediate 2, bent molecular structure II, K2CO3, Pd(PPh3)4, THF, and H2O were coupled via a Suzuki-Miyaura reaction. After separation and purification, the mixture was placed in a mixture of HCl, SnCl2·2H2O, and dry tetrahydrofuran, and the reaction was allowed to proceed from an ice-water bath to room temperature. After further separation and purification, molecular structure II was obtained. The synthetic route is shown below: ； R is a methyl group; n in molecular formula II is 1.

6. An application of a macrocyclic molecule of a type of modified carboxylic acid ester as described in claim 1 or claim 4, characterized in that: This macrocyclic molecule is used to fabricate light-emitting devices, which are electronic devices, and the electronic devices include functional thin film layers.

7. The application according to claim 6, characterized in that, The electronic device is an OLED device.

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