Preparation method of anthracene skeleton-containing deuterated micromolecular organic light-emitting transistor (OLET) material

Abstract

The invention relates to a synthesis method of several deuterated small molecular materials with anthracene skeletons, which starts from three small molecular materials with high mobility and strong luminescence, namely 2, 6-diphenyl anthracene (DPA), 2, 6-dinaphthyl anthracene (dNaAnt) and 2, 6-dianthryl naphthalene (2, 6-DAN), and realizes selective deuteration of different sites on an aromatic ring. The preparation method is used for preparing the organic light-emitting transistor with high mobility and strong luminescence. Various deuterated small molecules provided by the invention have important application potential and value in the field of preparation of devices such as organic light-emitting transistors (OLET) and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials, specifically relating to a method for synthesizing a series of selective anthracene-based deuterated small molecule materials with different sites. The compounds possess luminescent and conductive properties and can be used as active layer materials for organic light-emitting transistors. Background Technology

[0002] Multifunctional optoelectronic devices based on organic semiconductors have become an important development direction in the field of organic optoelectronics due to their multifunctionality, low cost, ease of fabrication, and good scalability. Exciting progress has been made in high-mobility organic semiconductors, broad-spectrum absorbing organic materials, and organic light-emitting materials, making the construction of high-performance organic optoelectronic devices possible. Examples include organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and organic light-emitting diodes (OLEDs). With the joint efforts of researchers in chemistry, physics, and microelectronics, the development of these devices is progressing steadily. Some of these devices (such as OLEDs) have already been commercialized or are in the process of commercialization. With the increasing demand for miniaturization and intelligence, the integration and multifunctionality of optoelectronic devices have become a current research hotspot.

[0003] Organic light-emitting transistors (OLETs) are the smallest integrated optoelectronic devices that combine the switching and amplification mechanisms of organic field-effect transistors (OFETs) with the electroluminescence characteristics of organic light-emitting diodes (OLEDs). This unique structure makes them ideal for developing next-generation display technologies and electrically pumped lasers for miniaturized photonic devices and circuits. However, the development of OLETs has been slow. In recent years, exciting progress has been made in high-mobility organic emitting semiconductors, the construction of high-performance OLETs, and the fabrication of novel multifunctional OLETs, which may represent a new stage in the development of OLETs and their related devices and circuits.

[0004] In the OLED industry, the practice of deuterating the molecules of the light-emitting layer material to improve device stability is widely accepted. Duan et al. (Huang, T., Wang, Q., Zhang, H. et al. Enhancing the efficiency and stability of blue thermally activated delayed fluorescence emitters by perdeuteration. Nat. Photon. 18, 516–523 (2024).) were the first to successfully employ a full molecular deuteration strategy, significantly improving the maximum external quantum efficiency and lifetime of blue thermally activated delayed fluorescence (TADF) OLED devices. Device testing showed that, compared to non-deuterated devices, deuterated devices exhibited lower turn-on voltage and higher current stability. Jung, S., Cheung, WL., Li, Sj. et al. Enhancing operationalstability of OLEDs based on subatomic modified thermally activated delayed fluorescence compounds. Nat Commun 14, 6481 (2023). Targeting deuterated diphenylamine and / or phenoxy groups on 5,9-dioxane-13b-boron heterocyclic [3,2,1-de]anthracene (BO), the results showed that the photostability of the compounds increased with increasing deuteration, and the operational stability of the devices also gradually improved.

[0005] Research on the deuteration lifetime of host materials, especially anthracene host materials, is limited. This invention, based on three high-mobility, strongly luminescent small molecule materials—2,6-diphenylanthracene (DPA), 2,6-dinathynylanthracene (dNaAnt), and 2,6-dinathynylnaphthalene (2,6-DAN)—involves several synthetic methods for small molecule materials with deuterated anthracene skeletons, achieving selective deuteration at different sites on the aromatic ring. These materials can be used to fabricate high-mobility, strongly luminescent organic light-emitting transistors, potentially improving device lifetime and current stability. Summary of the Invention

[0006] The purpose of this invention is to provide methods for synthesizing selectively deuterated anthracene-based small molecules 2,6-diphenylanthracene (DPA), 2,6-dinathynylanthracene (dNaAnt), and 2,6-dinathynylnaphthalene (2,6-DAN) at different sites. This provides organic semiconductor materials applicable to other organic semiconductor devices such as organic light-emitting transistors (OLETs). Through the anthracene skeleton and its associated aryl groups in the deuterated molecules, exciton-vibrational coupling generated during device light emission can be suppressed, thereby improving device lifetime and current stability.

[0007]

[0008]

[0009] Attached Figure Description

[0010] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0011] Figure 1 The image shows the hydrogen spectrum of the synthesized 2-deuterbromobenzene as described in Example 1.

[0012] Figure 2 The image shows the hydrogen spectrum of the synthesized 2-deuterium phenylboronic acid described in Example 1.

[0013] Figure 3 The synthesis of 2,6-bis[2-deuterbenzene]-anthracene (DPA-) as described in Example 1 d 2) The hydrogen spectrum.

[0014] Figure 4 The hydrogen spectrum of the synthesized 4-bromo-2,6-dideuterium-aniline described in Example 2.

[0015] Figure 5 The hydrogen spectrum of 2,6-dideuterium-aniline synthesized in Example 2 is shown.

[0016] Figure 6 The image shows the hydrogen spectrum of the synthesized 2,6-dideuterium-phenylboronic acid described in Example 2.

[0017] Figure 7 The synthesis of 2,6-bis[2,6-dideuterbenzene]-anthracene (DPA-) as described in Example 2 d 4) The hydrogen spectrum.

[0018] Figure 8 The DPA synthesized as described in Example 3- d 10 The hydrogen spectrum.

[0019] Figure 9 This is an illustration for the abstract of the instruction manual. Detailed Implementation

[0020] Unless otherwise defined, all technical and scientific terms in this application have the same meaning as generally understood by those skilled in the art in relation to the subject matter.

[0021] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to these examples.

[0022] Example 1: Synthesizing compound DPA- d Taking 2 as an example, its structure is as follows:

[0023] Step 1: Dehalogenate o-bromoiodobenzene to 2-deuterbromobenzene.

[0024]

[0025] Under an argon atmosphere, o-bromoiodobenzene (5 g, 17.7 mmol) was dissolved in a mixed solvent of THF and Et₂O (120 mL, 1:1). The temperature was lowered to -78 °C, and then magnesium isopropyl chloride (2 M THF, 9.0 mL, 18.0 mmol) was added dropwise to the solution. The reaction mixture was stirred at -78 °C for 2 h, followed by the addition of CD₃OD (2 g, 55.5 mmol). The reaction mixture was then slowly heated to room temperature, and 10% HCl aqueous solution (100 mL) was added. The mixture was stirred at room temperature for 30 min. The aqueous layer was then extracted with Et₂O (3 × 30 mL). The organic phases were combined, dried over Na₂SO₄, and diethyl ether was removed under reduced pressure. Finally, 2.3 g of pure 2-deuterium bromobenzene was obtained by vacuum distillation in 82% yield. 1 H NMR (600 MHz, Chloroform- d ) δ 7.50 (dd, J = 8.3, 1.2 Hz, 1H), 7.30 (ddd, J = 8.1, 6.9, 1.2Hz, 1H), 7.26 – 7.22 (m, 2H).

[0026] Step 2: Synthesize 2-deuterium phenylboronic acid.

[0027]

[0028] Under an argon atmosphere at -78 °C, 3.1 mL (2.1 M, 7.75 mmol) of n-butyllithium was added dropwise over 10 minutes to an anhydrous THF (60 mL) solution of o-bromodeuterium benzene (2 g, 12.66 mmol). The solution was stirred at -78 °C for 2 hours, and then triisopropyl borate (3.58 g, 18.98 mmol) dissolved in 8 mL of anhydrous THF was added dropwise to the reaction mixture, which was then heated to room temperature overnight. The mixture was then quenched with dilute hydrochloric acid (20%, 40 mL), and the reaction mixture was stirred at room temperature for 3 hours. The organic phase was extracted with Et₂O, washed twice with H₂O, and concentrated under reduced pressure. Finally, the crude product (viscous liquid) was concentrated under reduced pressure by adding petroleum ether, recrystallized from cold n-hexane, filtered, and dried to remove the white solid precipitated in n-hexane. This solid was then directly added to the next step without further purification (1.0 g, 70% yield). 1 H NMR (600 MHz, Chloroform- d ) δ 8.30 – 8.24 (m, 1H), 7.63 – 7.60 (m, 1H), 7.52 (ddd, J = 7.2, 4.5, 2.9 Hz, 2H).

[0029] Step 3: Synthesis of 2,6-bis[2-deuterbenzene]-anthracene (DPA- d 2).

[0030]

[0031] 2,6-bis(trifluoromethanesulfonic acid) anthracene (474 ​​mg, 1 mmol), phenylboronic acid-2- d (271 mg, 2.2 mmol) and Pd(PPh3)4 (463 mg, 0.05 mmol) were added to a 100 mL flask under an argon atmosphere. Then, ethanol (2 mL), toluene (8 mL), and K2CO3 (2 mL, 2M) aqueous solution were added, and the mixture was heated to 90 °C and stored overnight. After filtration, the solution was washed successively with triethylamine, dichloromethane, water, and ethanol. DPA- d 2 was a yellow solid (280 mg, separation yield 85%). 1 H NMR (600MHz, Chloroform- d ) δ 8.50 (s, 1H), 8.22 (s, 1H), 8.10 (d, J = 8.8 Hz, 1H),7.81 – 7.77 (m, 2H), 7.52 (dd,J = 7.9, 3.3 Hz, 2H), 7.41 (t, J = 7.5 Hz, 1H).

[0032] Example 2: Synthesizing compound DPA- d For example, 2 has the following structure.

[0033]

[0034] Step 1: Synthesize 3,5-ditrit-4-bromoaniline.

[0035]

[0036] 4-Bromoaniline (2.5 g, 14.5 mmol) was added to a dried 10 mL round-bottom flask, degassed, and purged three times with argon. Deuterated water (3 mL) and 37% DCl (1 mL) were added. The reaction was heated at 105 °C for 24 hours. After cooling to room temperature, the solvent was slowly and carefully evaporated. The hydrogen-deuterium exchange was repeated four times. The residue was diluted with 20 mL of water and neutralized with a saturated aqueous solution of Na₂CO₃ until pH > 11. The aqueous layer was extracted with dichloromethane. The combined organic layers were dried over Na₂SO₄, filtered, and evaporated under vacuum to give a pale brown solid product (2.4 g, 96%) with an isotopic purity of 97%. 1 H NMR (600 MHz, Chloroform- d ) δ 7.23 (d, J = 1.1 Hz, 2H), 3.67 (s, 2H).

[0037] Step 2: Debrominate 4-bromo-2,6-dideuterium-aniline.

[0038]

[0039] In a 50 mL round-bottom flask, 4-bromo-2,6-dideuterium-aniline (0.7 g, 4 mmol), PdCl₂ (14 mg, 0.08 mmol), and deionized water (20 mL) were added. The reaction mixture was stirred at room temperature for 2 min, and the resulting suspension was treated dropwise with 1,1,3,3-tetramethyldisiloxane (TMDs, 1.08 g, 8 mmol). The reaction was stirred for 1 h, and a second batch of TMDs (1.08 g, 8 mmol) was slowly added. The mixture was stirred for 2 h and extracted with Et₂O (10 mL). The aqueous layer was acidified with 2 M HCl to pH < 1 and concentrated under reduced pressure (100 mL MeOH was added to assist in water evaporation). The resulting off-white solid was dissolved in 20 mL MeOH and neutralized with NaOMe (216 mg, 4 mmol in 20 mL MeOH). The suspension was filtered and carefully concentrated under vacuum. 2,6-Dideuterium-aniline (149 mg, 39%) was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 3:1). Note: Solvent removal should be performed at low temperature to avoid product decomposition. 1 H NMR (600 MHz, Chloroform- d ) δ 7.17 (dd, J = 7.2, 1.3 Hz, 2H), 6.77 (t, J = 7.4 Hz, 1H), 3.94 – 3.14 (m, 2H).

[0040] Step 3: Synthesize 2,6-dideuterium phenylboronic acid.

[0041]

[0042] Hydrochloric acid (0.5 mL, 1.5 mmol, 3.0 equiv.) was added to a solution of 2,6-dideuterium-aniline (0.5 mmol, 1.0 equiv.) in methanol (1.0 mL), followed by the addition of water (0.5 mL). The mixture was stirred for 2 minutes. A NaNO2 solution was prepared by dissolving 35 mg of NaNO2 in water (0.25 mL) and stirring at 0–5 °C for 30 minutes. Tetrahydroxydiboron (381 mg, 1.5 mmol, 3.0 equiv.) was then added to methanol (1.0 mL). The mixture was stirred for 60 minutes. The crude mixture was extracted with DCM, concentrated, and washed with cold n-hexane to obtain the product. 1 H NMR (600 MHz, Chloroform- d ) δ 7.61(t,J = 7.4 Hz, 1H), 7.52 (d, J = 7.4 Hz, 2H), 3.77 (d, J = 18.9 Hz, 2H).

[0043] Step 4: Synthesis of 2,6-bis[2,6-dideuterene]-anthracene (DPA- d 4) (DPA- d 4).

[0044]

[0045] 474 mg (1 mmol) of 2,6-bis(trifluoromethanesulfonic acid)-anthracene, 273 mg (2.2 mmol) of 2,6-dideuterium phenylboronic acid, and 463 mg (0.05 mmol) of Pd(PPh3)4 were added to a 100 mL flask under an argon atmosphere. Then, 2 mL of ethanol, 8 mL of toluene, and 2 mL of 2M K2CO3 aqueous solution were added, and the mixture was heated to 90 °C and stored overnight. After filtration, the sample was washed successively with triethylamine, dichloromethane, water, and ethanol. DPA- d 4 was a yellow solid with a yield of 43% (142 mg). 1 H NMR (600 MHz, Chloroform- d ) δ 8.49 (s, 2H), 8.20 (d, J = 1.8 Hz, 2H), 8.09 (d, J = 8.8 Hz, 2H), 7.76 (dd, J = 8.7, 1.8 Hz, 2H), 7.51 (d, J = 7.4 Hz, 4H), 7.39 (t, J =7.4 Hz, 2H).

[0046] Example 3: Synthesizing compound DPA- d 10 For example, its structure is as follows.

[0047]

[0048] Steps: Generate DPA in one step using Suzuki coupling. d 10。

[0049]

[0050] 474 mg (1 mmol) of 2,6-bis(trifluoromethanesulfonic acid)-anthracene, 279 mg (2.2 mmol) of deuterated phenylboronic acid, and 463 mg (0.05 mmol) of Pd(PPh3)4 were added to a 100 mL flask under an argon atmosphere. Then, 2 mL of ethanol, 8 mL of toluene, and 2 mL of 2M K2CO3 aqueous solution were added, and the mixture was heated to 90°C and stored overnight. After filtration, the sample was washed successively with triethylamine, dichloromethane, water, and ethanol. DPA- d 10 It is a yellow solid with a yield of 85% (341 mg). 1 H NMR (600 MHz, Chloroform- d )δ 8.50 (s, 2H), 8.22 (d, J = 1.8 Hz, 2H), 8.10 (d, J = 8.7 Hz, 2H), 7.78 (dd, J = 8.7, 1.8 Hz, 2H).

[0051] Example 4: Synthesizing compound dNaAnt- d 14 For example, its structure is as follows.

[0052]

[0053] Step 1: Synthesize deuterated 2-naphthoboronic acid.

[0054]

[0055] Under an argon atmosphere at -78 °C, n-butyllithium (3.1 mL, 2.1 M, 7.75 mmol) was added dropwise over 10 minutes to a solution of deuterated 2-bromonaphthalene (2 g, 12.66 mmol) in anhydrous THF (60 mL). The solution was stirred at -78 °C for 2 hours, then trimethyl borate (1.97 g, 18.98 mmol) dissolved in 8 mL of dry THF was added dropwise to the reaction mixture, and the mixture was allowed to warm to room temperature overnight. The reaction mixture was quenched with dilute hydrochloric acid (20%, 40 mL), and stirred at room temperature for 3 hours. The organic phase was extracted with Et₂O, washed twice with H₂O, and concentrated under reduced pressure. Petroleum ether was added to the crude product (viscous liquid), the mixture was concentrated under reduced pressure, recrystallized from cold n-hexane, filtered, and dried to obtain a white solid precipitated in n-hexane, which was used directly without further purification (1.58 g, 70%).

[0056] Step 2: Generate DPA using Suzuki coupling. d10。

[0057]

[0058] 2,6-Di(trifluoromethanesulfonic acid)-anthracene (711 mg, 1.5 mmol), deuterated 2-naphthoboronic acid (805 mg, 4.5 mmol), tetra(triphenylphosphine)palladium(0) (0.09 mmol, 0.104 g), and potassium carbonate (6 mmol, 828 g) were added to a 250 mL three-necked round-bottom flask equipped with a magnetic rod under argon atmosphere. 30 mL of the mixed solvent (1,4-dioxane:ethanol:water, volume ratio 4:1:1) was added via syringe. The entire system was heated to 105 °C and incubated for 24 hours. The mixture was then filtered and washed sequentially with triethylamine, dichloromethane, water, and ethanol to obtain a crude product. The crude product was purified by recrystallization in 1,1,2,2-tetrachloroethane to give a yellow product (0.53 g, 80.0%). 1 H NMR (600 MHz, Chloroform- d ) δ 8.87(d, J = 27.6 Hz, 2H), 8.53 (s, 2H), 8.36 (s, 2H), 8.17 (d, J = 9.0 Hz, 2H).

Claims

1. The molecular structure of deuterated DPA and its application in organic semiconductor devices such as organic light-emitting transistors (OLEDs), characterized in that... It has the structure shown in Figure I below:

2. The deuterated dNaAnt molecular structure and its application in organic semiconductor devices such as organic light-emitting transistors (OLETs), characterized in that... It has the structure shown in Figure II below:

3. The deuterated 2,6-DAN molecular structure and its application in organic semiconductor devices such as organic light-emitting transistors (OLEDs), characterized in that... It has the structure shown in Figure III below:

4. The DPA as described in claim 1 d 2-molecule synthesis, characterized by Including step one, The DPA as described in claim 1 d 4-molecule synthesis, characterized by including step two, The DPA as described in claim 1 d 2. DPA- d 4. DPA- d 10 Molecular synthesis, characterized by including step three, The DPA as described in claim 1 d 18 Molecular synthesis, characterized by including step four:

5. The dNaAnt- as described in claim 2 d 8-molecule synthesis, characterized by Including step one, The dNaAnt- as described in claim 2 d 14 Molecular synthesis, characterized by including step two, The dNaAnt- as described in claim 2 d 8. dNaAnt- d 14 dNaAnt- d 22 Molecular synthesis, characterized by including step three:

6. The 2,6-DAN- as described in claim 3 d 6-molecule synthesis, characterized by Including step one, The 2,6-DAN- as described in claim 3 d 18 Molecular synthesis, characterized by including step two, The 2,6-DAN- as described in claim 3 d 6. 2,6-DAN- d 18 2,6-DAN- d 24 Molecular synthesis, characterized by including step three:

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