A compound containing a phosphate ester group, its preparation method, and its application in perovskite light-emitting devices.

Abstract

This invention provides a compound containing a phosphate ester group, its preparation method, and its application in perovskite light-emitting devices. The compound structure is shown in formula (I). This invention utilizes the strong electron affinity of the phosphate ester group to regulate charge carriers in the device, increasing the local carrier concentration on the perovskite film surface and promoting carrier radiative recombination. The phosphoxy groups in the compound have physical and / or chemical interactions with the perovskite components, influencing the kinetic behavior of different components during crystallization, regulating phase composition, passivating unsaturated lead defects in the perovskite lattice, reducing non-radiative energy loss, and improving the fluorescence quantum yield of the perovskite film. By introducing different substituents, the defect passivation effect can be adjusted. Devices obtained using the compound of this invention as an additive achieve high external quantum efficiency without significantly affecting the structure and luminescent properties of the perovskite itself.

Description

Technical Field

[0001] This invention belongs to the field of perovskite optoelectronic materials technology, specifically relating to a compound containing phosphate ester groups, its preparation method, and its application in perovskite light-emitting devices. Background Technology

[0002] Perovskite luminescent materials possess advantages such as inexpensive raw materials, a wide color gamut, pure light color, flexible and easily tunable luminescent properties, and low processing costs, making them a promising class of materials capable of meeting the needs of next-generation optoelectronic device applications. They are now widely used in the fabrication of electroluminescent devices. Perovskite luminescent devices typically consist of an ITO anode, a hole transport layer (HTL), an emissive layer (EL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode. The perovskite emissive layer is prepared using solution processing. For three-dimensional perovskite materials, radiative recombination is suppressed due to their relatively low exciton binding energy, resulting in low device efficiency. Introducing large organic ligands into the perovskite precursor solution enhances dielectric confinement and quantum confinement effects, promoting carrier radiative recombination and improving the external quantum efficiency of the device. However, due to the different kinetic behaviors of different perovskite components during film formation, the perovskite films obtained using this strategy often contain different phase compositions, which can be represented by the general formula L1 / L'2A. n-1 B n X 3n+1 This indicates that L and L' represent divalent and monovalent macrocations, respectively (e.g., 1,4-dimethylammonium ion P-PDA). 2+ Phenylacetamine ion (PEA) + A is a monovalent small cation (e.g., cesium ion Cs). + methylammonium ion MA + Formamidinium ion (FA) + B is a divalent cation (e.g., lead ion Pb). 2+ Tin ions Sn 2+ X is a monovalent anion (e.g., chloride ion Cl). - Bromide ions Br - Iodide ions - In the diagram, n represents the number of layers in the inorganic framework. Energy transfer exists between phases with different n values, but the presence of a large number of phases with small n values ​​hinders energy transfer efficiency. Reducing the proportion of phases with small n values ​​can promote energy transfer and improve device efficiency. Furthermore, numerous surface defects in perovskite films exacerbate nonradiative recombination energy loss. Reducing surface defects and enhancing radiative recombination on the perovskite surface are beneficial for improving device luminescence efficiency.

[0003] Currently, introducing additives that interact with perovskite components has been proven to be an effective strategy for improving the efficiency of perovskite light-emitting devices. This strategy can regulate the crystallization behavior of perovskite, reduce the formation of small n-value phases, and passivate perovskite surface defects. However, no additives have been reported that can simultaneously regulate carrier radiative recombination, and the efficiency of perovskite light-emitting devices needs further improvement. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a compound containing a phosphate ester group, a method for preparing the compound and its application in perovskite light-emitting devices. As a perovskite additive, the compound can not only regulate the crystallization behavior during the perovskite film formation process, reduce the formation of small n-value phases, and passivate surface defects of the thin film, but also promote the radiative recombination of charge carriers in the light-emitting device. By utilizing the synergistic effect of the two, the efficiency of the perovskite light-emitting device can be greatly improved.

[0005] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:

[0006] This invention provides a compound containing a phosphate ester group, the structure of which is shown in formula (I):

[0007]

[0008] Wherein, X1, X2, Y1, and Y2 are each independently selected from O or S; for example, the compound containing phosphate ester groups having the structures shown in formulas (II) to (IV) can have the following structures:

[0009]

[0010] and Each is independently selected from substituted or unsubstituted aromatic ring groups of C5 to C60, or substituted or unsubstituted aromatic heterocyclic groups of C3 to C60;

[0011] R1 and R2 are each independently selected from H, D, substituted or unsubstituted C1-C30 straight-chain hydrocarbon groups, substituted or unsubstituted C3-C30 branched hydrocarbon groups, substituted or unsubstituted C1-C30 haloalkane groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aromatic groups, or substituted or unsubstituted C5-C60 heteroaromatic groups; the non-adjacent carbon atoms of the straight-chain hydrocarbon groups and branched hydrocarbon groups can also be substituted by O or S atoms; the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0012] m is selected from integers from 0 to 2, n is selected from integers from 1 to 3, and the sum of m and n is 3.

[0013] In the above technical solution, preferably, the substituents in the substituted C5-C60 aromatic ring group and the substituted C3-C60 aromatic heterocyclic group are selected from H, D, F, Cl, Br, I, -CN, -NO2, C1-C30 straight-chain hydrocarbon groups, C3-C30 branched hydrocarbon groups, C1-C30 haloalkane groups, C3-C30 cycloalkyl groups, C6-C60 aromatic groups, or C5-C60 heteroaromatic groups;

[0014] Wherein, the R 1 R 2 and R 3 Each group is independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, C1-C30 straight-chain hydrocarbon groups, C3-C30 branched hydrocarbon groups, C1-C30 haloalkane groups, C3-C30 cycloalkyl groups, C6-C60 aromatic groups, or C5-C60 heteroaromatic groups; the heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S, and Se; R 1 R 2 and R 3 They can also interact through single bonds, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, Make connections; the L1′~L 12 Each group is independently selected from H, D, F, Cl, Br, I, -CN, -NO2, C1-C30 straight-chain hydrocarbon groups, C3-C30 branched hydrocarbon groups, C1-C30 haloalkane groups, C3-C30 cycloalkyl groups, C6-C60 aromatic groups, or C5-C60 heteroaromatic groups.

[0015] In the above technical solution, preferably, the... and Each group is independently selected from one of the groups shown in formulas 1 to 53:

[0016]

[0017]

[0018] L3 to L5 are each independently selected from H, D, F, Cl, Br, I, -CN, and -NO2. The following are possible classifications of hydrocarbon groups: C1-C30 straight-chain hydrocarbon groups, C3-C30 branched hydrocarbon groups, C1-C30 haloalkane groups, C3-C30 cycloalkyl groups, C6-C60 aromatic groups, or C5-C60 heteroaromatic groups; wherein the heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S, and Se; and the R... 1 R 2 and R 3 Consistent with the above limitations.

[0019] In the above technical solution, a further preferred option is, and Selected from substituted or unsubstituted aromatic ring groups of C5 to C48, or substituted or unsubstituted aromatic heterocyclic groups of C4 to C45;

[0020] More preferably, Selected from the following structures:

[0021]

[0022]

[0023] In the above structure, the dashed lines represent the connection points.

[0024] More preferably, Selected from the following structures:

[0025]

[0026] In the above structure, the dashed lines represent the connection points.

[0027] In the above technical solution, it is further preferred that the compound containing the phosphate ester group has one of the structures shown in Formula I-1 to Formula I-105:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034] This invention also provides a method for preparing a compound containing a phosphate ester group, comprising the following steps:

[0035] Method 1 includes the following steps:

[0036] a) An aryl Ar1 Grignard reagent (Formula Z) undergoes a nucleophilic substitution reaction with diethyl phosphite or diethyl thiophosphite (Formula M) to form a diaryl phosphorus oxide or diaryl phosphorus sulfide intermediate (Formula L).

[0037] b) An intermediate (formula N) of bromoarylphosphonate is prepared by reacting aryl Ar2 dihalides (formula S) with phosphate esters (formula P) via a Pd-catalyzed phosphorylation reaction.

[0038] c) The intermediate of diaryl phosphorus oxide or diaryl phosphorus sulfide (formula L) and the intermediate of bromoaryl phosphonate (formula N) are reacted by Pd-catalyzed phosphonylation to form the target compound (formula I) containing a phosphate ester group.

[0039]

[0040] Method 2 includes the following steps:

[0041] a) The halogenated aryl derivative Ar1 is first reacted with butyllithium to obtain a lithium salt (Formula A), and then reacted with bromoaryl phosphorus dichloride (Formula B) to undergo a substitution reaction, and then oxidized or sulfided to obtain bromoaryl phosphorus oxide or phosphorus sulfide derivatives (Formula C).

[0042] b) Under Pd catalysis, the target compound (I) containing a phosphate ester group was prepared by phosphorylation reaction of bromoaryl phosphorus oxide or phosphorus sulfide derivative (formula C) with phosphite (formula P).

[0043]

[0044] In the above structural formula:

[0045] ArylAr1- corresponds to the arylAr1- in formulas (II), (III) and (IV). unit;

[0046] ArylAr2- corresponds to the arylAr2- in formulas (II), (III) and (IV). unit;

[0047] The definitions of each substituent group, and m and n, are consistent with those in equation (I) above, and will not be repeated here.

[0048] Preferably, in method one:

[0049] In step a), the reaction temperature is 0–25°C and the time is 1.5–8 hours.

[0050] In step b), the reaction temperature is 50-68℃, the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the reaction time is 1.5-12h.

[0051] In step c), the reaction temperature is 64–115 °C, the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the reaction time is 8–16 h.

[0052] In Method Two:

[0053] In step a), the oxidizing agent is hydrogen peroxide and the sulfiding agent is S8.

[0054] In step b), the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the time is 3 to 16 hours.

[0055] The present invention also provides the use of the compound containing phosphate ester groups as shown in formula (I) above as a perovskite additive.

[0056] The present invention also provides a perovskite light-emitting device, comprising an anode, a cathode, and a perovskite thin film located between the anode and the cathode; the perovskite thin film comprising a compound containing a phosphate ester group as shown in formula (I) above.

[0057] The present invention does not impose any particular limitation on the structure of the perovskite light-emitting device, and any conventional perovskite light-emitting device well known to those skilled in the art can be used. Those skilled in the art can select and adjust the structure according to the application, quality requirements and product requirements. The preferred structure of the perovskite light-emitting device of the present invention includes: a substrate; an anode disposed on the substrate; a perovskite thin film layer disposed on the anode; and a cathode disposed on the perovskite thin film layer.

[0058] The thickness of the substrate is preferably 0.3-0.7 mm, more preferably 0.4-0.6 mm. The present invention does not impose any special restrictions on the selection of the substrate, and any substrate of conventional electroluminescent devices known to those skilled in the art can be used. Those skilled in the art can select and adjust the substrate according to the application, quality requirements and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0059] According to the present invention, the anode is preferably a material that is easy to inject holes, more preferably a conductive metal or a conductive metal oxide, and even more preferably an indium tin oxide.

[0060] The perovskite thin film layer is preferably a light-emitting layer; the light-emitting layer comprises a compound containing phosphate ester groups as shown in formula (I) above; the compound containing phosphate ester groups as shown in formula (I) provided by the present invention is used as an additive to constitute the perovskite electroluminescent layer. The perovskite light-emitting layer is preferably prepared by a solution spin coating process. During the spin coating process, a solution containing the compound containing phosphate ester groups as shown in formula (I) is added dropwise, and after the spin coating is completed, the resulting film is annealed to obtain the perovskite light-emitting layer.

[0061] To improve the performance and efficiency of the device, the thin film between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The thin film between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. This invention does not impose particular limitations on the materials, thicknesses, and fabrication processes of the hole injection layer, hole transport layer, electron blocking layer, perovskite electroluminescent layer, hole blocking layer, electron injection layer, and electron transport layer; materials and thicknesses well known to those skilled in the art can be selected and adjusted, and appropriate processes can be selected based on the characteristics of the materials.

[0062] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum and silver, with aluminum being the most preferred.

[0063] The beneficial effects of this invention are:

[0064] This invention provides a compound containing a phosphate ester group, which is used as a perovskite additive, with the structure shown in formula (I). Compared with the prior art, this invention can utilize the strong electron affinity of the phosphate ester group to regulate the carriers in perovskite light-emitting devices, increase the local carrier concentration on the surface of the perovskite film, and promote carrier radiative recombination. The phosphoxy groups in this compound structure have physical and / or chemical interactions with the perovskite components, which can affect the kinetic behavior of different components during crystallization, regulate the phase composition in the perovskite film, passivate unsaturated lead defects in the perovskite lattice, reduce non-radiative energy loss, and improve the fluorescence quantum yield of the perovskite film. By introducing different substituents, the defect passivation effect can be further adjusted.

[0065] Experimental results show that using perovskite films modified with compounds containing phosphate groups as additives, as the emitting layer of electroluminescent devices, can achieve high external quantum efficiency without significantly affecting the structure and luminescence properties of the perovskite itself. This invention provides structural design ideas for the development of additive materials for high-performance perovskite optoelectronic devices. Attached Figure Description

[0066] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0067] Figure 1 The above is the 1H NMR spectrum of compound I-7 containing phosphate ester groups prepared in Example 4 of this invention.

[0068] Figure 2 The phosphorus spectrum of compound I-7 containing phosphate ester groups prepared in Example 4 of this invention.

[0069] Figure 3 This is the mass spectrum of compound I-7 containing a phosphate ester group, prepared in Example 4 of the present invention.

[0070] Figure 4 This is a graph showing the relationship between the external quantum efficiency and current density of the electroluminescent device using compound I-7 as a perovskite additive in Example 38 of the present invention. Detailed Implementation

[0071] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0072] To further illustrate the present invention, the following describes in detail, with reference to embodiments, the preparation of a compound containing a phosphate ester group, its use as a perovskite additive, and its application in an electroluminescent device.

[0073] All reagents used in the following examples are commercially available.

[0074] Example 1

[0075] The reaction equation is as follows:

[0076]

[0077] Diethyl phosphite (0.85 mL, 6.5 mmol) was dissolved in 10 mL of diethyl ether. After cooling the reaction solution to 0 °C, a diethyl ether solution of magnesium phenyl bromide Grignard reagent (5.2 mL, 15.6 mmol) was added dropwise to the reaction flask. The reaction solution was stirred at room temperature for 5 hours. The reaction solution was then poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with diethyl ether, and the combined organic phases were dried over Na2SO4. After complete removal of the solvent, the product was purified by silica gel column chromatography (using petroleum ether / ethyl acetate = 2:1 as eluent) to give the product diphenylphosphine oxide (0.95 g, yield 72%) as a white solid. 1HNMR (500MHz, CDCl3) δ8.03 (d, J = 480.7Hz, 1H), 7.81-7.73 (m, 4H), 7.57-7.7.52 (m, 2H), 7.47-7.40 (m, 4H).

[0078] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.32 g, 1.1 mmol), bisphenylphosphine oxide (0.20 g, 1.0 mmol), N-methylmorpholine (0.15 g, 1.5 mmol), and tetra(triphenylphosphine)palladium (0.058 g, 0.05 mmol) were dissolved in 7 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.36 g of pure white crystalline product I-1, yield: 86%. 1 HNMR (500MHz, CDCl3) δ 7.91-7.89 (m, 4H), 7.78-7.75 (m, 4H), 7.56-7.51 (m, 6H), 4.21-4.11 (m, 4H), 1.36 (t, J = 7.1Hz, 6H). 31 PNMR(202.4MHz, DMSO)δ24.08,15.99ppm.

[0079] Example 2

[0080] The reaction equation is as follows:

[0081]

[0082] Under an argon atmosphere, magnesium shavings (0.53 g, 21.0 mmol) and a small grain of iodine were placed in a dry three-necked flask. p-Bromotoluene (3.40 g, 20.0 mmol) was dissolved in 100 mL of dry diethyl ether in a constant-pressure dropping funnel. Approximately 15 mL of the p-Bromotoluene diethyl ether solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (1.19 mL, 9.1 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na2SO4. After complete solvent removal, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate (2:1 eluent) to give bis(4-methylphenyl)phosphine oxide as a white solid (3.14 g, 65% yield). 1HNMR (500MHz, CDCl3) δ 8.03 (d, J = 486.6 Hz, 1H), 7.59 (dd, J = 13.3, 8.4 Hz, 4H), 7.46 (dd, J = 13.5, 2.2 Hz, 4H), 2.37 (s, 6H).

[0083] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.32 g, 1.1 mmol), bis(4-methylphenyl)phosphine oxide (0.23 g, 1.0 mmol), N-methylmorpholine (0.15 g, 1.5 mmol), and tetra(triphenylphosphine)palladium (0.058 g, 0.05 mmol) were dissolved in 7 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.35 g of pure white crystalline product I-2, yield: 78%. 1 HNMR(500MHz, CDCl3)δ7.88-7.83(m,2H),7.70-7.66(m,2H),7.52(dd,J=11.8,8.5Hz,4 H), 7.42 (dd, J = 8.6, 2.3Hz, 4H), 4.22-4.12 (m, 4H), 2.39 (s, 6H), 1.36 (t, J = 7.1Hz, 6H). 31 P NMR (202.4MHz, DMSO) δ23.86, 15.91ppm.

[0084] Example 3

[0085] The reaction equation is as follows:

[0086]

[0087] Under an argon atmosphere, magnesium shavings (0.53 g, 21.0 mmol) and a small grain of iodine were placed in a dry three-necked flask. p-fluorobromobenzene (3.50 g, 20.0 mmol) was dissolved in 100 mL of dry THF in a constant-pressure dropping funnel. Approximately 15 mL of the p-fluorobromobenzene THF solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (1.19 mL, 9.1 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na2SO4. After complete solvent removal, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate (2:1 eluent) to give bis(4-fluorophenyl)phosphine oxide as a white solid (3.19 g, 67% yield).

[0088] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.64 g, 2.2 mmol), bis(4-fluorophenyl)phosphine oxide (0.48 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.69 g of a pure white crystalline product I-6, yield: 77%.

[0089] Example 4

[0090] The reaction equation is as follows:

[0091]

[0092] Under an argon atmosphere, magnesium shavings (0.37 g, 15.0 mmol) and a small grain of iodine were added to a dry three-necked flask. p-Bromochlorobenzene (2.49 g, 13.0 mmol) was dissolved in dry tetrahydrofuran (80 mL) in a constant-pressure dropping funnel. Approximately 10 mL of the p-bromochlorobenzene THF solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (0.56 mL, 4.3 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na2SO4. After complete solvent removal, the mixture was purified by silica gel column chromatography (using petroleum ether / ethyl acetate = 1:1 as eluent) to give the product bis(4-chlorophenyl)phosphine oxide as a white solid (2.11 g, 60% yield).1 HNMR (500MHz, CDC13) δ 8.07 (d, J = 486.6 Hz, 1H), 7.63 (dd, J = 13.3, 8.4 Hz, 4H), 7.50 (dd, J = 13.5, 2.2 Hz, 4H).

[0093] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.32 g, 1.1 mmol), bis(4-chlorophenyl)phosphine oxide (0.27 g, 1.0 mmol), N-methylmorpholine (0.15 g, 1.5 mmol), and tetra(triphenylphosphine)palladium (0.058 g, 0.05 mmol) were dissolved in 7 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was separated by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1 / 2). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.39 g of pure white crystalline product I-7, yield: 80%. 1HNMR (500MHz, DMSO) δ7.94-7.89 (m, 2H), 7.76-7.72 (m, 2H), 7.64-7.67 (m, 8H), 4.02-4.06 (m, 4H), 1.24 (t, J = 7.1Hz, 6H). 31P NMR (202.4MHz, DMSO) δ24.12, 16.01ppm. HRMS(ESI,m / z)calcd for C 22 H 23 Cl2O4P2[M+H]+483.0449; Found: 483.0429.

[0094] Example 5

[0095] The reaction equation is as follows:

[0096]

[0097] Under an argon atmosphere, magnesium shavings (0.53 g, 21.0 mmol) and a small grain of iodine were placed in a dry three-necked flask. p-Dibromobenzene (4.72 g, 20.0 mmol) was dissolved in 100 mL of dry THF in a constant-pressure dropping funnel. Approximately 15 mL of the p-dibromobenzene THF solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (1.19 mL, 9.1 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na2SO4. After complete solvent removal, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate (2:1 eluent) to give bis(4-bromophenyl)phosphine oxide as a white solid (5.1 g, 71% yield).

[0098] Bis(4-bromophenyl)phosphine oxide (1.44 g, 4.0 mmol) and diethyl (4-iodophenyl)phosphonate (1.50 g, 4.4 mmol) were dissolved in anhydrous THF (40 mL). The mixture was purged three times, and palladium acetate (54 mg, 0.24 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.28 g, 0.48 mmol), potassium acetate (84 mg, 0.88 mmol), and triethylamine (0.42 mL, 6.6 mmol) were added. The mixture was heated to 68 °C and stirred for 3 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:5) to give 1.44 g of product I-8, with a yield of 63%.

[0099] Example 6

[0100] The reaction equation is as follows:

[0101]

[0102] Under an argon atmosphere, magnesium shavings (0.27 g, 10.5 mmol) and a small grain of iodine were placed in a dry three-necked flask. 4-Bromotriphenylamine (3.24 g, 10.0 mmol) was dissolved in 60 mL of dry diethyl ether and placed in a constant-pressure dropping funnel. Approximately 8 mL of the 4-bromotriphenylamine diethyl ether solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (0.6 mL, 4.6 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 60 mL of NH₄Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na₂SO₄. After the solvent was completely removed, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate = 1:1 eluent to obtain bis(4-diphenylaminophenyl)phosphine oxide, which was a white solid (3.27 g, yield 61%).

[0103] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.64 g, 2.2 mmol), bis(4-diphenylaminophenyl)phosphine oxide (1.08 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.92 g of a pale yellow solid, I-13, in 62% yield.

[0104] Example 7

[0105] The reaction equation is as follows:

[0106]

[0107] Compound I-8 (1.14 g, 2.0 mmol) and bisphenylphosphine oxide (0.89 g, 4.4 mmol) were dissolved in anhydrous THF (20 mL). The mixture was purged three times, and palladium acetate (54 mg, 0.24 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.28 g, 0.48 mmol), potassium acetate (84 mg, 0.88 mmol), and triethylamine (0.63 mL, 9.9 mmol) were added. The mixture was heated to 74 °C and stirred for 5 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:5) to give product I-151.1 g, yield: 68%.

[0108] Example 8

[0109] The reaction equation is as follows:

[0110]

[0111] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of (4-bromophenyl)bis(trimethylyl)boron (4.05 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, 4-bromophenyl phosphorus dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.2 g of (4-bromophenyl)bis(4-(ditrimethylbenzylboryl)phenyl)phosphine oxide, a white solid. The two-step yield was 38%.

[0112] (4-Bromophenyl)bis(4-(dimethyltrimethylboryl)phenyl)phosphine oxide (1.7 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:2) to give I-161.3 g, a white solid, yield: 74%.

[0113] Example 9

[0114] The reaction equation is as follows:

[0115]

[0116] Under an argon atmosphere, magnesium shavings (0.53 g, 21.0 mmol) and a small grain of iodine were placed in a dry three-necked flask. 3,4-Difluorobromobenzene (3.86 g, 20.0 mmol) was dissolved in 100 mL of dry THF in a constant-pressure dropping funnel. Approximately 15 mL of the 3,4-difluorobromobenzene THF solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (1.19 mL, 9.1 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH₄Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na₂SO₄. After the solvent was completely removed, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate = 2:1 eluent to obtain bis(3,4-difluorophenyl)phosphine oxide as a white solid (3.4 g, yield 63%).

[0117] Bis(3,4-difluorophenyl)phosphine oxide (1.09 g, 4.0 mmol), diethyl (4-bromophenyl)phosphonate (1.29 g, 4.4 mmol), N-methylmorpholine (0.60 g, 6.0 mmol), and tetra(triphenylphosphine)palladium (0.24 g, 0.20 mmol) were dissolved in 30 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 1.4 g of I-29 white solid, yield: 74%.

[0118] Example 10

[0119] The reaction equation is as follows:

[0120]

[0121] Under an argon atmosphere, magnesium shavings (0.53 g, 21.0 mmol) and a small grain of iodine were placed in a dry three-necked flask. 3,4-Dichlorobromobenzene (4.52 g, 20.0 mmol) was dissolved in 100 mL of dry THF in a constant-pressure dropping funnel. Approximately 15 mL of the 3,4-dichlorobromobenzene THF solution was added to the three-necked flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was heated under reflux for 2 hours. The reaction solution was cooled to 0°C, and diethyl phosphite (1.19 mL, 9.1 mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction solution was poured into 100 mL of NH₄Cl aqueous solution. The mixture was extracted three times with dichloromethane, and the combined organic phases were dried over Na₂SO₄. After the solvent was completely removed, the product was purified by column chromatography on a silica gel column using petroleum ether / ethyl acetate = 2:1 eluent to obtain bis(3,4-dichlorophenyl)phosphine oxide as a white solid (4.5 g, yield 66%).

[0122] Bis(3,4-difluorophenyl)phosphine oxide (1.02 g, 3.0 mmol), diethyl (4-bromophenyl)phosphonate (0.96 g, 3.3 mmol), N-methylmorpholine (0.50 g, 5 mmol), and tetra(triphenylphosphine)palladium (0.24 g, 0.20 mmol) were dissolved in 30 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 1.3 g of I-30 white solid, yield: 77%.

[0123] Example 11

[0124] The reaction equation is as follows:

[0125]

[0126] Diethyl thiophosphite (1.0 g, 6.5 mmol) was dissolved in 10 mL of diethyl ether. After cooling the reaction solution to 0 °C, a solution of magnesium phenyl bromide Grignard reagent in diethyl ether (5.2 mL, 15.6 mmol) was added dropwise to the reaction flask. The reaction solution was stirred at room temperature for 7 hours. The reaction solution was then poured into 100 mL of NH₄Cl aqueous solution. The mixture was extracted three times with diethyl ether, and the combined organic phases were dried over Na₂SO₄. After complete removal of the solvent, the product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 2:1) to give the product diphenylphosphine sulfide (0.95 g, yield 67%) as a white solid.

[0127] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.64 g, 2.2 mmol), diphenylphosphine sulfide (0.44 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.62 g of a pure white crystalline product, I-39, in 73% yield.

[0128] Example 12

[0129] The reaction equation is as follows:

[0130]

[0131] Diethyl thiophosphite (1.0 g, 6.5 mmol) was dissolved in 10 mL of diethyl ether. After cooling the reaction solution to 0 °C, a solution of 4-methylphenyl magnesium bromide Grignard reagent in diethyl ether (45 mL, 15.6 mmol) was added dropwise to the reaction flask. The reaction solution was stirred at room temperature for 7 hours. The reaction solution was then poured into 100 mL of NH4Cl aqueous solution. The mixture was extracted three times with diethyl ether, and the combined organic phases were dried over Na2SO4. After complete removal of the solvent, the product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1) to give bis(4-methylphenyl)phosphine sulfide (1.14 g, yield 71%) as a white solid.

[0132] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.64 g, 2.2 mmol), bis(4-methylphenyl)phosphine sulfide (0.49 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.63 g of pure white crystalline product I-40, yield: 69%.

[0133] Example 13

[0134] The reaction equation is as follows:

[0135]

[0136] Under an argon atmosphere, 1.13 g (4.0 mmol) of 4-bromoiodobenzene and 0.82 g (4.4 mmol) of diethyl trithiophosphate were dissolved in 20 mL of anhydrous THF. The mixture was purged three times, and palladium acetate (46 mg, 0.20 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.22 g, 0.40 mmol), potassium acetate (45 mg, 0.44 mmol), and triethylamine (0.65 mL, 10 mmol) were added. The mixture was heated to 64 °C and stirred for 3 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 0.99 g of (4-bromophenyl) trithiophosphate, in 73% yield.

[0137] Under an argon atmosphere, diethyl (4-bromophenyl)trithiophosphate (0.75 g, 2.2 mmol), diphenylphosphine sulfide (0.73 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1 / 2). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.66 g of pure white solid I-52, yield: 69%.

[0138] Example 14

[0139] The reaction equation is as follows:

[0140]

[0141] Under an argon atmosphere, diethyl (3-bromophenyl)phosphonate (0.64 g, 2.2 mmol), bisphenylphosphine oxide (0.40 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 14 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1 / 1). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.66 g of I-65, a pure white solid, in 79% yield.

[0142] Example 15

[0143] The reaction equation is as follows:

[0144]

[0145] 1.13 g (4.0 mmol) of p-bromoiodobenzene and 1.00 g (4.0 mmol) of dihexyl phosphite were dissolved in anhydrous THF (30 mL). The mixture was purged three times, and palladium acetate (54 mg, 0.24 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.28 g, 0.48 mmol), potassium acetate (84 mg, 0.88 mmol), and triethylamine (0.63 mL, 9.9 mmol) were added. The mixture was heated to 68 °C and stirred for 3 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 1.4 g of (4-bromophenyl)phosphite, in 85% yield.

[0146] Under an argon atmosphere, dihexyl (4-bromophenyl)phosphonate (0.97 g, 2.2 mmol), bisphenylphosphine oxide (0.40 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 14 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 0.84 g of pure white solid I-77, yield: 80%.

[0147] Example 16

[0148] The reaction equation is as follows:

[0149]

[0150] 1.13 g (4.0 mmol) of p-bromoiodobenzene and 1.14 g (4.0 mmol) of di(2-(2-methoxyethoxy)ethyl) phosphite were dissolved in anhydrous THF (30 mL). The mixture was purged three times, and palladium acetate (54 mg, 0.24 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.28 g, 0.48 mmol), potassium acetate (84 mg, 0.88 mmol), and triethylamine (0.63 mL, 9.9 mmol) were added. The mixture was heated to 68 °C and stirred for 3 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 1.5 g of (4-bromophenyl) phosphate, with a yield of 87%.

[0151] bis(2-(2-methoxyethoxy)ethyl)phosphonate

[0152] Under an argon atmosphere, (4-bromophenyl) phosphate (0.97 g, 2.2 mmol), bisphenylphosphine oxide (0.40 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 14 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:2) to give 0.84 g of I-80 white solid, yield: 80%.

[0153] Example 17

[0154] The reaction equation is as follows:

[0155]

[0156] Diethyl phosphite (0.85 mL, 6.5 mmol) was dissolved in 10 mL of diethyl ether. After cooling the reaction solution to 0 °C, a solution of 4-pyridyl magnesium bromide Grignard reagent in diethyl ether (5.2 mL, 15.6 mmol) was added dropwise to the reaction flask. The reaction solution was stirred at room temperature for 5 hours. The reaction solution was then poured into 50 mL of NH4Cl aqueous solution. The mixture was extracted three times with diethyl ether, and the combined organic phases were dried over Na2SO4. After complete removal of the solvent, the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:2) to give bis(4-pyridyl)phosphine oxide (0.90 g, yield 68%) as a white solid.

[0157] Under an argon atmosphere, diethyl (4-bromophenyl)phosphonate (0.64 g, 2.2 mmol), bis(4-pyridyl)phosphine oxide (0.41 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:3). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.60 g of I-82 white solid, yield: 72%.

[0158] Example 18

[0159] The reaction equation is as follows:

[0160]

[0161] To a solution of 2-bromo-9,9-dimethylfluorene (2.73 g, 10 mmol) in anhydrous THF (100 mL), n-butyllithium (4 mL, 2.5 M) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 30 minutes. Then, 4-bromophenylphosphine dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.3 g of (4-bromophenyl)bis(9,9-dimethylfluorene-2-yl)phosphine oxide, a white solid. The two-step yield was 57%.

[0162] (4-Bromophenyl)bis(9,9-dimethylfluorene-2-yl)phosphine oxide (1.16 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-841.0 g, a white solid, yield: 81%.

[0163] Example 19

[0164] The reaction equation is as follows:

[0165]

[0166] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 2.89 g (10 mmol) of 3-bromo-5,5-dimethyldibenzosiloxane (THF), and the mixture was stirred at -78°C for 30 minutes. Then, 1.17 g (4.5 mmol) of 4-bromophenyl dichloride was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.2 g of (4-bromophenyl)bis(9,9-dimethyl-9-silazfluoren-2-yl)phosphine oxide, a white solid. The two-step yield was 51%.

[0167] (4-Bromophenyl)bis(9,9-dimethyl-9-silazfluoren-2-yl) (1.24 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-85 1.13 g, a white solid, yield: 83%.

[0168] Example 20

[0169] The reaction equation is as follows:

[0170]

[0171] To a solution of 100 mL of anhydrous THF containing 1.97 g (10 mmol) of 2-bromobenzofuran, n-butyllithium (4 mL, 2.5 M) was added dropwise at -78 °C. The mixture was stirred at -78 °C for 30 min, followed by slow addition of 1.17 g (4.5 mmol) of 4-bromophenyl dichloride. The mixture was then slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 1.88 g of (4-bromophenyl)bis(benzofuran-2-yl)phosphine oxide, a white solid. The two-step yield was 43%.

[0172] (4-bromophenyl)bis(benzofuran-2-yl)phosphine oxide (0.87 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-860.85 g, a white solid, yield: 86%.

[0173] Example 21

[0174] The reaction equation is as follows:

[0175]

[0176] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 2-bromobenzothiophene (2.13 g, 10 mmol), and the mixture was stirred at -78°C for 30 min. Then, 4-bromophenyl phosphorus dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane, and an aqueous hydrogen peroxide solution (30%, 2.0 mL) was added at 0°C and stirred for 3 h. After concentration to remove the solvent, the product was separated by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 2.3 g of (4-bromophenyl)bis(benzothiophene-2-yl)phosphine oxide, a white solid. The two-step yield was 49%.

[0177] (4-bromophenyl)bis(benzothiophene-2-yl)phosphine oxide (0.94 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-870.8 g, a white solid, yield: 78%.

[0178] Example 22

[0179] The reaction equation is as follows:

[0180]

[0181] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 2-bromobenzopyrrole (2.24 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, 4-bromophenyl phosphorus dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane, and an aqueous hydrogen peroxide solution (30%, 2.0 mL) was added at 0°C and stirred for 3 hours. After concentration to remove the solvent, the mixture was separated by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 2.0 g of (4-bromophenyl)bis(benzopyrrole-2-yl)phosphine oxide, a white solid. The two-step yield was 41%.

[0182] (4-bromophenyl)bis(benzopyrrole-2-yl)phosphine oxide (0.98 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-880.9 g, a white solid, yield: 82%.

[0183] Example 23

[0184] The reaction equation is as follows:

[0185]

[0186] To a solution of 2.47 g (10 mmol) of 3-bromodibenzofuran in 100 mL of anhydrous THF, add 4 mL (2.5 M) of n-butyllithium dropwise at -78 °C and stir for 30 min at -78 °C. Then slowly add 1.17 g (4.5 mmol) of 4-bromophenyl dichloride. Allow the mixture to slowly warm to room temperature over 2 hours. Add saturated NaCl and extract the reaction mixture three times with diethyl ether. Dry the combined extracts with anhydrous magnesium sulfate, filter, and concentrate under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 2.3 g of (4-bromophenyl)bis(dibenzofuran-3-yl)phosphine oxide, a white solid. The two-step yield was 43%.

[0187] (4-bromophenyl)bis(dibenzofuran-3-yl)phosphine oxide (1.07 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 1.0 g of product I-89, a white solid, in 83% yield.

[0188] Example 24

[0189] The reaction equation is as follows:

[0190]

[0191] To a solution of 2.63 g (10 mmol) of 3-bromodibenzothiophene in 100 mL of anhydrous THF, add 4 mL (2.5 M) of n-butyllithium dropwise at -78 °C and stir for 30 min at -78 °C. Then, slowly add 1.17 g (4.5 mmol) of 4-bromophenyl dichloride. Allow the mixture to slowly warm to room temperature over 2 hours. Add saturated NaCl, and extract the reaction mixture three times with diethyl ether. Dry the combined extracts with anhydrous magnesium sulfate, filter, and concentrate under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 2.5 g of (4-bromophenyl)bis(dibenzothiophene-3-yl)phosphine oxide, a white solid. The two-step yield was 44%.

[0192] (4-bromophenyl)bis(dibenzothiophene-3-yl)phosphine oxide (1.14 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-900 0.98 g, a white solid, in 78% yield.

[0193] Example 25

[0194] The reaction equation is as follows:

[0195]

[0196] To a solution of 2-bromo-N-ethylcarbazole (2.74 g, 10 mmol) in anhydrous THF (100 mL), n-butyllithium (4 mL, 2.5 M) was added dropwise at -78 °C, and the mixture was stirred at -78 °C for 30 minutes. Then, 4-bromophenylphosphine dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.5 g of (4-bromophenyl)bis(N-ethylcarbazole-2-yl)phosphine oxide, a white solid. The two-step yield was 59%.

[0197] (4-Bromophenyl)bis(N-ethylcarbazole-2-yl)phosphine oxide (1.18 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-911.1 g, a white solid, yield: 82%.

[0198] Example 26

[0199] The reaction equation is as follows:

[0200]

[0201] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 2-bromo-10-ethyl-9,9-dimethyl-9,10-dihydroacrylidine (3.16 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, 4-bromophenyl phosphorus dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.65 g of (4-bromophenyl)bis(10-ethyl-9,9-dimethyl-9,10-dihydroacrylin-2-yl)phosphine oxide, a white solid. The two-step yield was 54%.

[0202] (4-Bromophenyl)bis(10-ethyl-9,9-dimethyl-9,10-dihydroacrylin-2-yl)phosphine oxide (1.35 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-921.2 g, a white solid, yield: 82%.

[0203] Example 27

[0204] The reaction equation is as follows:

[0205]

[0206] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 2.90 g (10 mmol) of 3-bromo-10-ethyl-10H-phenoxazine, and the mixture was stirred at -78°C for 30 minutes. Then, 1.17 g (4.5 mmol) of 4-bromophenyl phosphorus dichloride was slowly added. The mixture was then slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 2.6 g of (4-bromophenyl)bis(10-ethyl-10H-phenoxazine-3-yl)phosphine oxide, a white solid. The two-step yield was 42%.

[0207] (4-Bromophenyl)bis(10-ethyl-10H-phenoxazin-3-yl)phosphine oxide (1.25 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-930.99 g, a white solid, yield: 73%.

[0208] Example 28

[0209] The reaction equation is as follows:

[0210]

[0211] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (100 mL) solution of 3-bromo-10-ethyl-10H-phenthiazide (3.06 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, 4-bromophenyl phosphorus dichloride (1.17 g, 4.5 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 2.0 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 2.7 g of (4-bromophenyl)bis(10-ethyl-10H-phenthiazin-3-yl)phosphine oxide, a white solid. The two-step yield was 41%.

[0212] (4-Bromophenyl)bis(10-ethyl-10H-phenthiazin-3-yl)phosphine oxide (1.31 g, 2.0 mmol) and diethyl phosphite (0.33 g, 2.4 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-941.2 g, a white solid, yield: 85%.

[0213] Example 29

[0214] The reaction equation is as follows:

[0215]

[0216] 1.6 g (4.0 mmol) of 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene and 0.61 g (4.4 mmol) of diethyl phosphite were dissolved in anhydrous toluene (15 mL). The mixture was purged three times, and then tetra(triphenylphosphine)palladium (0.23 g, 0.2 mmol) and triethylamine (0.92 mL, 6.6 mmol) were added. The mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 1:1) to give 1.33 g of (7-bromo-9,9-dimethyl-9H-fluorene-2-yl)phosphonate diethyl ester, in 81% yield.

[0217] Under an argon atmosphere, diethyl (7-bromo-9,9-dimethyl-9H-fluoren-2-yl)phosphonate (0.90 g, 2.2 mmol), bisphenylphosphine oxide (0.40 g, 2.0 mmol), N-methylmorpholine (0.30 g, 3.0 mmol), and tetra(triphenylphosphine)palladium (0.12 g, 0.10 mmol) were dissolved in 15 mL of anhydrous toluene, and the mixture was heated to 100 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:2). Further purification by recrystallization using n-hexane and dichloromethane as solvents yielded 0.80 g of I-99 white solid, yield: 75%.

[0218] Example 30

[0219] The reaction equation is as follows:

[0220]

[0221] Under an argon atmosphere, magnesium shavings (0.32 g, 13 mmol) and a small grain of iodine were added to a dry three-necked flask. p-Dibromobenzene (3.1 g, 13 mmol) was dissolved in dry tetrahydrofuran (80 mL) and added to approximately 8 mL of the solution in the flask. After the brownish-yellow color faded, the remaining solution was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours. Phenylene phosphorus dichloride (0.68 mL, 5 mmol) was slowly added dropwise, and the reaction was allowed to proceed overnight. The resulting reaction solution was poured into a large volume of ammonium chloride aqueous solution. The mixture was extracted three times with dichloromethane and concentrated to obtain a yellow viscous liquid. This liquid was dissolved in dichloromethane (10 mL), and then hydrogen peroxide aqueous solution (30%, 1.5 mL) was added and stirred for 3 hours. After concentration to remove the solvent, the mixture was separated by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to obtain 1.4 g of bis(4-bromophenyl)phenylphosphine oxide as a white solid, with a yield of 62%.

[0222] Bis(4-bromophenyl)phenylphosphine oxide (0.87 g, 2.0 mmol) and diethyl phosphite (0.72 g, 4.4 mmol) were dissolved in anhydrous THF (20 mL). The mixture was purged three times, and palladium acetate (27 mg, 0.12 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.14 g, 0.24 mmol), potassium acetate (42 mg, 0.44 mmol), and triethylamine (0.42 mL, 6.6 mmol) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:5) to give I-101 0.82 g, yield: 75%.

[0223] Example 31

[0224] The reaction equation is as follows:

[0225]

[0226] At -78°C, n-butyllithium (8 mL, 2.5 M hexane) was added dropwise to an anhydrous THF (100 mL) solution of dibromobenzene (4.72 g, 20 mmol). The mixture was stirred at -78°C for 30 minutes, and then freshly distilled phosphorus trichloride (0.58 mL, 6.67 mmol) was slowly added. The mixture was allowed to slowly warm to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1) to give 8.68 g of tribromophenylphosphine as a white solid, yield: 87%.

[0227] Tribromophenylphosphine (2.5 g, 5 mmol) was dissolved in 30 mL of dichloromethane, and hydrogen peroxide aqueous solution (30%, 1.0 mL) was added at 0 °C. The mixture was stirred for 3 h, concentrated to remove the solvent, and then separated by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to obtain 2.45 g of tri(4-bromophenyl)phosphine oxide as a white solid with a yield of 95%.

[0228] Phosphorus tris(4-bromophenyl)oxide (1.03 g, 2.0 mmol) and diethyl phosphite (1.08 g, 6.6 mmol) were dissolved in anhydrous THF (20 mL). The mixture was purged three times, and palladium acetate (41 mg, 0.18 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.20 g, 0.36 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (0.63 mL, 9.9 mmol) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:7) to give I-1021.33 g, yield: 73%.

[0229] Example 32

[0230] The reaction equation is as follows:

[0231]

[0232] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (80 mL) solution of 2,6-dibromonaphthalene (2.86 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, phenylphosphine dichloride (0.81 g, 4.5 mmol) was slowly added. The mixture was slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane, and an aqueous hydrogen peroxide solution (30%, 1.0 mL) was added at 0°C. The mixture was stirred for 3 hours, concentrated to remove the solvent, and then separated by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give 2.4 g of bis(6-bromonaphthalene-2-yl)(phenyl)phosphine oxide, a white solid. The two-step yield was 44%.

[0233] Bis(6-bromonaphth-2-yl)(phenyl)phosphine oxide (1.07 g, 2.0 mmol) and diethyl phosphite (0.66 g, 4.8 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (54 mg, 0.24 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.28 g, 0.48 mmol), potassium acetate (64 mg, 0.66 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) to give I-1030.9 g, a white solid, yield: 69%.

[0234] Example 33

[0235] The reaction equation is as follows:

[0236]

[0237] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (80 mL) solution of 2,6-dibromonaphthalene (2.86 g, 10 mmol), and the mixture was stirred at -78°C for 30 minutes. Then, freshly distilled phosphorus trichloride (0.46 g, 3.3 mmol) was slowly added. The mixture was slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 0.8 mL) was added at 0°C, and the mixture was stirred for 3 hours. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to give 2.4 g of tris(6-bromonaphthalene-2-yl)phosphorus oxide, a white solid. Two-step yield: 44%.

[0238] Tris(6-bromonaphthyl-2-yl)phosphine oxide (1.07 g, 2.0 mmol) and diethyl phosphite (0.91 g, 6.6 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (81 mg, 0.36 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.42 g, 0.64 mmol), potassium acetate (85 mg, 0.88 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:7) to give I-104 0.97 g, a white solid, yield: 58%.

[0239] Example 34

[0240] The reaction equation is as follows:

[0241]

[0242] At -78°C, n-butyllithium (4 mL, 2.5 M) was added dropwise to an anhydrous THF (75 mL) solution of 3.52 g (10 mmol) of 2,7-dibromo-9,9-dimethylfluorene. The mixture was stirred at -78°C for 30 minutes, followed by slow addition of freshly distilled phosphorus trichloride (0.46 g, 3.3 mmol). The mixture was then slowly heated to room temperature over 2 hours. Saturated NaCl was added, and the reaction mixture was extracted three times with diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (dichloromethane / n-hexane = 1:1). The resulting white solid was dissolved in 60 mL of dichloromethane. Hydrogen peroxide aqueous solution (30%, 0.8 mL) was added at 0 °C and stirred for 3 h. After concentration to remove the solvent, silica gel column chromatography (petroleum ether / ethyl acetate = 1:1) was performed to obtain 3.8 g of tris(7-bromo-9,9-dimethylfluorene-2-yl)phosphine oxide, a white solid. The two-step yield was 44%.

[0243] Tris(7-bromo-9,9-dimethylfluorene-2-yl)phosphine oxide (1.73 g, 2.0 mmol) and diethyl phosphite (0.91 g, 6.6 mmol) were dissolved in anhydrous THF (15 mL). The mixture was purged three times, and palladium acetate (81 mg, 0.36 mmol), 1,1'-bis(diphenylphosphine)ferrocene (0.42 g, 0.64 mmol), potassium acetate (85 mg, 0.88 mmol), and triethylamine (1 mL) were added. The mixture was heated to 74 °C and stirred for 8 hours. After the reaction mixture cooled to room temperature, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1:7) to give I-105 1.01 g, a white solid, yield: 51%.

[0244] Device Examples

[0245] 1. Preparation of perovskite precursor solution

[0246] Styrene-based ammonium bromide (PEABr), formamidine bromide (FABr), lead bromide (PbBr2), and chloromethylamine (MACl) were dissolved in a mixed solvent of N,N dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a molar ratio of 2:4:5:0.5, wherein Pb... 2+ The molar concentration is 0.2 mol per liter. After stirring the solution for 10 hours, let it stand, filter it, and then use it.

[0247] 2. Fabrication of perovskite light-emitting devices using solution spin coating + vacuum evaporation process

[0248] Under a nitrogen atmosphere, polyvinylcarbazole (PVK) dissolved in chlorobenzene at a concentration of 10 mg / mL was spin-coated onto indium tin oxide supported on a glass substrate. The mixture was annealed at 120°C for 30 minutes. Subsequently, a perovskite luminescent layer was spin-coated at 8000 rpm. Ten seconds after spin-coating the perovskite precursor solution, ethyl acetate containing the invented compound was added dropwise. The mixture was annealed at 80°C for 30 minutes, and then transferred to a 5×10⁻⁶ plate. -4 Under a vacuum of Pa, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF), and aluminum (Al) cathodes are deposited sequentially to obtain a perovskite electroluminescent device, in which PVK and TPBi serve as the hole transport layer and electron transport layer, respectively, and its structural formula is shown below:

[0249]

[0250] The specific device structure (device structure 1) is: ITO / PVK (40nm) / EML (~50nm) / TPBi (55nm) / LiF (1.2 nm) / Al (100nm).

[0251] Example 35

[0252] Using Formula I-1 from Example 1 as the subject of this study, Formula I-1 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0253] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0254] Example 36

[0255] Using Formula I-2 from Example 2 as the subject of this study, Formula I-2 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0256] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0257] Example 37

[0258] Using Formula I-6 from Example 3 as the subject of this study, Formula I-6 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0259] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0260] Example 38

[0261] Using Formula I-7 from Example 4 as the subject of this study, Formula I-7 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0262] Refer to Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention. The relationship between the external quantum efficiency and current density of the prepared electroluminescent devices is shown in the figure. Figure 4 .

[0263] Example 39

[0264] Using Formula I-8 from Example 5 as the subject of this study, Formula I-8 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0265] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0266] Example 40

[0267] Using Formula I-13 from Example 6 as the subject of this study, Formula I-13 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0268] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0269] Example 41

[0270] Using Formula I-15 from Example 7 as the subject of this study, Formula I-15 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0271] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0272] Example 42

[0273] Using Formula I-16 from Example 8 as the subject of this study, Formula I-16 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0274] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0275] Example 43

[0276] Using Formula I-29 from Example 9 as the subject of this study, Formula I-29 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0277] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0278] Example 44

[0279] Using Formula I-30 from Example 10 as the subject of this study, Formula I-30 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0280] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0281] Example 45

[0282] Using Formula I-39 from Example 11 as the subject of this study, Formula I-39 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0283] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0284] Example 46

[0285] Using Formula I-40 from Example 12 as the subject of this study, Formula I-40 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0286] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0287] Example 47

[0288] Using Formula I-52 from Example 13 as the subject of this study, Formula I-52 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0289] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0290] Example 48

[0291] Using Formula I-65 from Example 14 as the subject of this study, Formula I-65 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0292] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0293] Example 49

[0294] Using Formula I-77 from Example 15 as the subject of this study, Formula I-77 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0295] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0296] Example 50

[0297] Using Formula I-80 from Example 16 as the subject of this study, Formula I-80 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0298] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0299] Example 51

[0300] Using Formula I-82 from Example 17 as the subject of this study, Formula I-82 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0301] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0302] Example 52

[0303] Using Formula I-84 from Example 18 as the subject of this study, Formula I-84 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0304] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0305] Example 53

[0306] Using Formula I-85 from Example 19 as the subject of this study, Formula I-85 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0307] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0308] Example 54

[0309] Using Formula I-86 from Example 20 as the subject of this study, Formula I-86 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0310] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0311] Example 55

[0312] Using Formula I-87 from Example 21 as the subject of this study, Formula I-87 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0313] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0314] Example 56

[0315] Using Formula I-88 from Example 22 as the subject of this study, Formula I-88 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0316] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0317] Example 57

[0318] Using Formula I-89 from Example 23 as the subject of this study, Formula I-89 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0319] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0320] Example 58

[0321] Using Formula I-90 from Example 24 as the subject of this study, Formula I-90 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0322] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0323] Example 59

[0324] Using Formula I-91 from Example 25 as the subject of this study, Formula I-91 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0325] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0326] Example 60

[0327] Using Formula I-92 from Example 26 as the subject of this study, Formula I-92 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0328] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0329] Example 61

[0330] Using Formula I-93 from Example 27 as the subject of this study, Formula I-93 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0331] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0332] Example 62

[0333] Using Formula I-94 from Example 28 as the subject of this study, Formula I-94 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, then dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0334] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0335] Example 63

[0336] Using Formula I-99 from Example 29 as the subject of this study, Formula I-99 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0337] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0338] Example 64

[0339] Using Formula I-101 from Example 30 as the subject of this study, Formula I-101 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0340] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0341] Example 65

[0342] Using Formula I-102 from Example 31 as the subject of this study, Formula I-102 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0343] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0344] Example 66

[0345] Using Formula I-103 from Example 32 as the subject of this study, Formula I-103 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, being dropped onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0346] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0347] Example 67

[0348] Using Formula I-104 from Example 33 as the subject of this study, Formula I-104 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0349] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0350] Example 68

[0351] Using Formula I-105 from Example 34 as the subject of this study, Formula I-105 was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0352] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0353] Comparative Example 1

[0354] Using ethyl acetate without additives as the experimental material, ethyl acetate was dropped onto the film surface during the perovskite light-emitting layer deposition process as an antisolvent. The organic hole transport layer was prepared by solution spin coating, and the organic electron transport layer was prepared by vacuum evaporation. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1", and the resulting device was tested.

[0355] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0356] Comparative Example 2

[0357] Using triphenylphosphine oxide (TPPO) without phosphate ester groups as the experimental subject, TPPO was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0358] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0359] Comparative Example 3

[0360] Using chlorinated triphenylphosphine oxide (Cl-TPPO) without phosphate ester groups as the experimental subject, Cl-TPPO was dissolved in ethyl acetate at a concentration of 0.75 mg / mL and used as an antisolvent during the perovskite light-emitting layer film formation process, dripping it onto the film surface. The organic hole transport layer was prepared using a solution spin-coating process, and the organic electron transport layer was prepared using a vacuum evaporation process. A perovskite electroluminescent device was fabricated using the structure described in "Device Structure 1," and the resulting device was tested.

[0361] See Table 1, which provides the performance parameters of the perovskite electroluminescent devices prepared according to the embodiments of the present invention.

[0362] Table 1 Performance parameters of the device provided in the embodiments of the present invention

[0363]

[0364] Note: The start-up voltage in the table is for a brightness of 1 cd / m². -2The driving voltage of the device; the maximum external quantum efficiency is obtained from the current-voltage curve and electroluminescence spectrum of the device according to the calculation method described in the literature (Jpn.J.Appl.Phys.2001, 40, L783); the half-width at half-maximum is the peak width at half the peak height of the electroluminescence spectrum at room temperature, that is, the distance between the two points where the straight line parallel to the bottom of the peak is drawn through the midpoint of the peak height and intersects the two sides of the peak.

[0365] As shown in Table 1, the perovskite electroluminescent devices prepared from the compounds containing phosphonate groups provided in this invention generally exhibit high device efficiency. Compared to Comparative Example 1 without additives, the peak value of the electroluminescence spectrum changes by only 2 nm, and the full width at half maximum (FWHM) remains essentially unchanged, indicating negligible alteration to the device's luminescent properties. By rationally selecting substituents to enhance the defect passivation effect of the phosphono groups, a perovskite electroluminescent device achieving a maximum external quantum efficiency of 25.1% was realized (see Table 1). Figure 4 ).

[0366] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A compound containing a phosphate ester group, characterized in that, It has one of the structures shown in Formula I-1 to Formula I-105: 。 2. A method for preparing the compound containing a phosphate ester group as described in claim 1, characterized in that, Includes the following steps: The compound containing phosphate ester groups has the structure shown in formula (I): Formula (I) In equation (I), X1, X2, Y1, Y2, , R1 and R2 all correspond to the corresponding groups on the specific compounds in claim 1, m is 2 and n is 1; Method 1 includes the following steps: a) The Grignard reagent containing an aryl Ar1 group shown in Formula Z undergoes a nucleophilic substitution reaction with diethyl phosphite or diethyl thiophosphite shown in Formula M to form a diaryl phosphorus oxide or diaryl phosphorus sulfide intermediate shown in Formula L. b) The aryl Ar2 dihalide shown in Formula S and the phosphate ester shown in Formula P are reacted with a Pd-catalyzed phosphorylation reaction to prepare the intermediate of the bromoaryl phosphonate shown in Formula N. c) The diaryl phosphorus oxide or diaryl phosphorus sulfide intermediate shown in Formula L and the bromoaryl phosphonate intermediate shown in Formula N are subjected to a Pd-catalyzed phosphonylation reaction to form the target compound containing a phosphate ester group shown in Formula (I). Method 2 includes the following steps: a) A haloaryl containing an Ar1 group is first subjected to lithium halide exchange with butyllithium to obtain the lithium salt shown in Formula A, and then subjected to a substitution reaction with the brominated aryl phosphorus dichloride shown in Formula B, and then oxidized or sulfided to obtain the brominated aryl phosphorus oxide or phosphorus sulfide derivative shown in Formula C. b) Under Pd catalysis, the target compound containing phosphate ester group shown in formula (I) was prepared by phosphorylation of the bromoaryl phosphorus oxide or phosphorus sulfide derivative shown in formula C with the phosphite shown in formula P. In the above structural formula: X1, X2, Y1, Y2, Ar1, Ar2, R1, and R2 all correspond to the corresponding groups on the specific compounds in claim 1, m is 2, and n is 1; The aryl Ar1 group corresponds to the one in formula (I) unit; ArylAr2 corresponds to the formula (I) unit.

3. The method for preparing the compound containing a phosphate ester group according to claim 2, characterized in that, In Method 1: In step a), the reaction temperature is 0~25℃ and the time is 1.5~8 h; In step b), the reaction temperature is 50-68℃, the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the reaction time is 1.5-12 h. In step c), the reaction temperature is 64~115℃, the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the reaction time is 8~16 h. In Method 2: In step a), the oxidizing agent is hydrogen peroxide and the sulfiding agent is S8; In step b), the catalytic system is palladium acetate / dppf / potassium acetate / triethylamine / THF or Pd(PPh3)4 / N-methylmorpholine / toluene, and the time is 3~16 h.

4. The use of the compound containing a phosphate ester group as a perovskite additive according to claim 1.

5. A perovskite light-emitting device, comprising an anode, a cathode, and a perovskite thin film layer located between the anode and the cathode, characterized in that, The perovskite thin film layer includes the compound containing phosphate groups as described in claim 1 as a perovskite additive.

6. The perovskite light-emitting device according to claim 5, characterized in that, The perovskite thin film layer includes a light-emitting layer, wherein the light-emitting layer includes the compound containing phosphate ester groups as a perovskite additive as described in claim 1.

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