Full-conjugated carbazolyl pinene chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic photoelectric functional materials, and discloses a full-conjugate carbazolyl pinene chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material as well as a preparation method and application thereof. According to the tetradentate platinum (II) or palladium (II) phosphorescent material disclosed by the invention, a pinene structure with large stereo steric hindrance, a donor carbazolyl structure derivative with anions and different acceptor structure units are introduced, so that the tetradentate platinum (II) or palladium (II) phosphorescent material has a large conjugate plane and a high conjugation degree, and an aggregation state-induced emission enhancement effect is realized; according to the palladium (II) complex phosphorescent material disclosed by the invention, the concentration quenching effect and exciton annihilation caused by long service life are effectively inhibited, and the photoluminescence quantum efficiency of the palladium (II) complex phosphorescent material is improved to the greatest extent, so that the phosphorescent quantum yield of the material is remarkably improved, and the piezo-chromic red shift effect is also realized; the vapor deposition method under specific conditions is applied to the luminescent layer of the electroluminescent device, and has great potential in the aspects of recording, data storage, sensors and the like.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic functional materials technology, specifically to an asymmetric chiral fully conjugated carbazole pinene tetradentate platinum(II) or palladium(II) complex phosphorescent material with aggregation-induced emission and pressure-induced color change properties, and its application in electroluminescent devices, pressure sensors or electrochromic devices. Background Technology

[0002] Phosphorescent materials based on heavy metal complexes can simultaneously collect singlet and triplet excitons to achieve a unified internal quantum efficiency (PLQY). OLEDs using these phosphorescent metal complexes as emitters have demonstrated excellent device performance, along with high external quantum efficiency (EQE), high color purity, and long operating life, indicating their potential applications in full-color displays and solid-state lighting. Current research on phosphorescent metal complexes mainly focuses on iridium (Ir), platinum (Pt), and palladium (Pd). Among them, platinum (II) or palladium (II) complexes possess special geometric configurations that can be used to construct bidentate, tridentate, and even tetradentate ligands. Different tooth configurations significantly influence their photophysical properties. Bidentate complexes are very easy to modify due to their molecular conformation, and the rotation between molecules leads to nonradiative transitions that consume the energy of the excited state. Therefore, new molecular structures need to be designed to suppress these nonradiative transitions, thereby enhancing the luminescence performance of the complexes. Tridentate ligands are more rigid than bidentate ligands, their molecular conformation is less easily modified, and their nonradiative transitions are smaller. Tetradentate platinum(II) or palladium(II) ligands exhibit superior rigidity compared to trimentate ligands, significantly reducing nonradiative transitions and demonstrating excellent stability. Palladium(II) complexes, in particular, typically exhibit a much weaker strong spin-orbit coupling (SOC) effect and lack an effective radiative decay process from T1 to S0, leading to concentration quenching and a severe decrease in efficiency. Therefore, most of them possess long decay lifetimes at room temperature. Furthermore, palladium(II) complexes often exhibit thermally accessible metallic center dd states, resulting in excited-state structural distortion and nonradiative decay. With finely designed structures, palladium(II) complexes can also exhibit strong phosphorescence. Palladium(II) complexes demonstrate sufficient potential as efficient and stable emitters, and their applications in OLEDs for full-color displays and solid-state lighting have been demonstrated.

[0003] Carbazole-based pinene-based luminescent materials are easy to synthesize and chemically modify, possessing high electron affinity, luminous efficiency, and excellent electrochemical and optical properties, thus finding applications in electronic devices such as OLEDs, OPVs, OFETs, and chemical biosensors. Carbazole is a heterocyclic compound whose structure can be extensively modified. Carbazole derivatives have attracted considerable attention due to their low raw material cost, ease of structural modification, good hole transport performance, and good stability. Carbazole derivatives typically exhibit strong charge transfer and hole transport capabilities in their molecular structures. Introducing inexpensive and high-performance carbazole groups into metal complexes can yield more easily synthesized and commercially viable organic optoelectronic materials. These materials are characterized by bipolar charge carrier transport and generally high photoluminescence efficiency. Bipolar carbazole is used as a luminescent material due to its high fluorescence efficiency. Such materials should exhibit good stability, low ionization potential, a specific band gap between HOMO and LUMO, and a good equilibrium process for introducing charge carriers during repeated doping, which significantly improves the operating efficiency of systems based on these materials. Carbazole derivatives typically exhibit suitable energy levels, good charge transport properties, and the high triplet energy required by the host material. The combination of electron-donating carbazole units and electron-deficient units produces materials that can become highly efficient emitters. TADF luminescent materials are an important application of carbazole derivatives; donor-acceptor carbazole derivatives are a class of compounds exhibiting TADF luminescence properties. Pinene is a sterically hindered compound containing a saturated aliphatic ring, possessing unique structural characteristics and excellent solubility. It can be prepared from aromatic acetaldehydes and enaldehydes, and has attracted increasing attention in many fields such as materials chemistry, supramolecular chemistry, and organocatalysis. In this invention patent, we synthesized an asymmetric chiral, fully conjugated carbazole-based pinene tetradentate platinum(II) or palladium(II) complex using p-bromoacetophenone and o-nitrobenzoic acid as raw materials. Introducing pinene, which has significant steric hindrance, into the structure enhances the solubility of the complex, greatly reducing the difficulty of the coordination reaction. It also increases the steric hindrance of the complex, reducing non-radiative transitions during excitation, thereby suppressing π-π electron accumulation, weakening concentration quenching, and ultimately improving luminescence efficiency. The electroluminescent device fabricated using this invention employs a vapor deposition method under specific conditions, offering advantages such as low cost, simple operation, stable chemical properties, and high efficiency. Furthermore, the material exhibits significant aggregation-induced emission and piezochromic properties, making it applicable to sensors, anti-counterfeiting, storage, and display fields. Summary of the Invention

[0004] The purpose of this invention is to provide an asymmetric chiral fully conjugated carbazole pinene tetradentate platinum(II) or palladium(II) complex phosphorescent material with aggregation-induced emission and pressure-induced color change properties, which has excellent photoelectric properties, stability, film-forming properties, solubility, and is easy to prepare and low in cost, and its application in the fields of electroluminescence, pressure sensing or electrochromic devices, so as to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a phosphorescent material based on a fully conjugated carbazole-based pinene chiral tetradentate platinum(II) or palladium(II) complex. Specifically, the complex is an asymmetric chiral fully conjugated tetradentate complex based on a fully conjugated carbazole-based pinene ligand, and the general structural formula of the complex is the compound represented by the following formula (I):

[0006] in, ; R1 is one of a straight-chain, branched, or cyclic aliphatic alkyl, substituted alkyl, aryl, or substituted aryl group having 1 to 18 carbon atoms; R2 is one of a hydrogen atom, cyano, nitro, acyl, a straight-chain, branched, or cyclic aliphatic alkyl, substituted alkyl, alkoxy, aryloxy, alkylthio, arylthio, aliphatic amino, aromatic amino, aryl, or substituted aryl group.

[0007] The present invention also provides a method for preparing the phosphorescent material of the fully conjugated carbazole pinene chiral tetradentate platinum(II) or palladium(II) complex as described above, comprising the following steps: S1, the carbazo-pinene compound shown in formula (1) and the halo-aryl phenyl-substituted aromatic heterocyclic compound shown in formula (2) are dissolved in an organic solvent and reacted at 110~140 °C for 20~40 h in the presence of a catalyst, ligand and base to obtain the chiral asymmetric fully conjugated tetradentate ligand based on carbazo-pinene as shown in formula (3). ; S2. The asymmetric chiral fully conjugated carbazole-based pinene tetradentate ligands and potassium tetrachloroplatinate or palladium acetate as shown in formula (3) are dissolved in an organic solvent, a catalyst is added, and the mixture is stirred at room temperature in the dark for 6 to 12 hours under nitrogen protection. Then the temperature is raised to 120 to 150 °C and reacted for 18 to 72 hours to obtain the asymmetric chiral fully conjugated carbazole-based pinene tetradentate platinum (II) or palladium (II) complex phosphorescent material as shown in formula (I).

[0008] Where X is Br or I; M is Pt or Pd; ; R1 is one of a straight-chain, branched, or cyclic aliphatic alkyl, substituted alkyl, aryl, or substituted aryl group having 1 to 18 carbon atoms; R2 is one of a hydrogen atom, cyano, nitro, acyl, a straight-chain, branched, or cyclic aliphatic alkyl, substituted alkyl, alkoxy, aryloxy, alkylthio, arylthio, aliphatic amino, aromatic amino, aryl, or substituted aryl group.

[0009] Further, in step S1, the molar ratio of the compound shown in formula (1), the compound shown in formula (2), the organic solvent, the catalyst, the ligand, and the base is 1:1-3:10-500:0.01-2:0.03-5:1-10.

[0010] Further, in step S1, the catalyst is one of cuprous iodide, cuprous bromide, Pd(PPh3)4, Pd(dba)3, and Pd(OAc)2; the ligand is one of 2,2,6,6-tetramethyl-3,5-heptadecylone, triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, and L-proline; the organic solvent is one of toluene, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, and 1,4-dioxane; and the base is one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, cesium carbonate, and potassium trimethylsilanolate.

[0011] Further, in step S2, the molar ratio of the asymmetric chiral fully conjugated carbazoyl pinene tetradentate ligand, potassium tetrachloroplatinate or palladium acetate, organic solvent, and catalyst shown in formula (3) is 1:1-1.5:100-1000:1-5.

[0012] Further, in step S2, the catalyst is one of potassium acetate, sodium acetate, ammonium acetate, tetrabutylammonium bromide, and tetrabutylammonium chloride; the organic solvent is one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetic acid, propionic acid, and butyric acid.

[0013] Further, in step S1, the preparation method of the carbazole pinene derivative shown in formula (1) includes the following process route: .

[0014] Specifically, the following steps are included: S1-1. p-Bromoacetophenone is dissolved in a pyridine organic solvent as a raw material, and an iodine pyridine solution is added. The mixture is reacted at 100~120℃ for 5~10h to obtain a pyridine salt derivative as shown in formula (1-1); the molar ratio of p-bromoacetophenone, pyridine, and iodine is 1:5~100:0.5~1. S1-2, pyridine salt derivatives, enaldehyde derivatives and organic salts are dissolved in an organic solvent and refluxed for 10-20 h to obtain bromopinene derivatives as shown in formula (1-2); the molar ratio of pyridine salt derivatives, enaldehyde derivatives, organic salts and organic solvents is 1:1-1.5:2-3:10-500, wherein the organic salt is one of ammonium acetate, sodium acetate and potassium acetate; wherein the organic solvent is one of toluene, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, methanol, ethanol and dimethyl sulfoxide; S1-3, bromopinene derivatives, and nitrobenzene compounds, in the presence of a palladium catalyst, cuprous iodide, and a base, dissolve in organic solvents at 160-190 °C. The reaction is carried out at ℃ for 20-30 h to obtain nitrophenyl pinene derivatives as shown in formula (1-3); the molar ratio of bromopinene derivatives, nitrobenzene compounds, palladium catalyst, cuprous iodide, base, and organic solvent is 1:1-7:0.01-0.1:0.1-1:1-5:10-500; the palladium catalyst is one of tetrakis(triphenylphosphine)palladium, tris(dibenzylacetone)palladium, di(triphenylphosphine)palladium dichloride, and 1,1'-di(diphenylphosphine)ferrocenepalladium dichloride; the base is one of potassium carbonate, sodium carbonate, sodium tert-butoxide, and potassium tert-butoxide; the organic solvent is one of toluene, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, and dimethyl sulfoxide. S1-4, nitrophenylpinene derivatives and triphenylphosphine are dissolved in an organic solvent and refluxed for 20-30 h to obtain carbazole-based pinene derivatives as shown in formula (1); the molar ratio of the nitrophenylpinene derivatives, triphenylphosphine and organic solvent is 1:1-5:10-50, and the organic solvent is one of toluene, N,N-dimethylformamide, o-dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane and dimethyl sulfoxide.

[0015] Furthermore, the preparation methods of the halo-substituted aromatic heterocyclic compounds shown in formula (2) include multiple routes.

[0016] Specifically, one embodiment of the present invention is as follows: The raw materials, m-halophenylboronic acid or m-dihalophenyl, and aromatic heterocyclic compounds are dissolved in an organic solvent and obtained by suzuki coupling as shown in formula (2); the aromatic heterocyclic compound is one of 2-haloaromatic heterocyclic compound, 2-aromatic heterocyclic boric acid, benzothiazole, and benzoxazole.

[0017] The structural formulas of the m-halophenylboronic acid, m-dihalophenylene, 2-haloaromatic heterocyclic compound, and 2-aromatic heterocyclic boronic acid are as follows: ; Where X and Y are independently Br or I; The molar ratio of m-halophenylboronic acid or m-dihalophenylene, aromatic heterocyclic compound, catalyst, base, and organic solvent is 1:0.5-1:0.01~0.1:0.25~5:10~500. The catalyst is one of tetratetraphenylphosphine palladium, bis(triphenylphosphine)palladium dichloride, and 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride. The base is one of potassium carbonate, sodium carbonate, silver carbonate, sodium tert-butoxide, and potassium tert-butoxide. The organic solvent is one of toluene, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, and acetonitrile.

[0018] The method for preparing the halo-substituted aromatic heterocyclic compound shown in formula (2), and other embodiments of the present invention are as follows: The other steps are the same as S1-1 and S1-2, except that the raw material p-bromoacetophenone is replaced with m-bromoacetophenone.

[0019] The present invention also provides the application of the fully conjugated carbazole pinene chiral tetradentate platinum(II) or palladium(II) complex phosphorescent materials as described above in electroluminescent devices.

[0020] Furthermore, the fully conjugated carbazole pinene-based chiral tetradentate platinum(II) or palladium(II) complex phosphorescent material is used in the light-emitting layer of an electroluminescent device.

[0021] The present invention also provides the application of the fully conjugated carbazole pinene chiral tetradentate platinum(II) or palladium(II) complex phosphorescent materials as described above in pressure sensor devices and pressure-sensitive devices.

[0022] This invention relates to the application of carbazole-based pinene compounds with large steric hindrance to tetradentate platinum(II) or palladium(II) phosphorescent complexes. By introducing different substituents to modify the aromatic rings on the host ligand, fully conjugated tetradentate platinum(II) or palladium(II) complex phosphorescent materials with a large steric hindrance structure are obtained. These asymmetric chiral fully conjugated carbazole-based pinene tetradentate platinum(II) or palladium(II) complex phosphorescent materials exhibit strong aggregation-induced emission properties. When applied to the emitting layer of organic electroluminescent devices, the large steric hindrance of the pinene structure effectively suppresses concentration quenching caused by intermolecular aggregation. Its saturated alicyclic structure effectively regulates the solubility of the complex, achieving highly efficient phosphorescent devices. Meanwhile, the asymmetric chiral fully conjugated carbazole pinene tetradentate platinum(II) or palladium(II) complex phosphorescent materials, due to the introduction of freely rotating substituents, can change the intermolecular stacking structure through external forces to achieve changes in emission color. These materials have good piezochromic properties and can be potentially applied in fields such as data recording, data storage, pressure sensors and pressure-sensitive devices.

[0023] Compared with the prior art, the beneficial effects of the present invention are: The phosphorescent asymmetric chiral fully conjugated carbazole-based pinene tetradentate platinum(II) or palladium(II) complexes of this invention, by introducing a sterically hindered pinene structure containing a saturated aliphatic ring encapsulating a palladium core, a donor carbazole-based structural derivative with an anion, and different acceptor structural units onto the ligand, possess a large conjugated plane and high conjugation degree, achieving aggregation-induced emission. This effectively suppresses the concentration quenching effect and exciton annihilation caused by long lifetimes, maximizing the improvement of the luminescence efficiency of palladium(II) complex phosphorescent materials, and also achieving a pressure-induced color-shifting effect. In this invention, compounds containing active groups are used to replace halogen atoms, further improving the solubility, hole transport capability, and thermal stability of the complexes. In addition, the introduction of these groups can generate certain steric effects, thereby reducing the interaction between the luminescent centers of the complexes, reducing the self-quenching phenomenon of triplet excitons, and improving the luminescence performance of the material.

[0024] The synthesis method of the complexes of this invention is simple and easy to purify. The electroluminescent devices prepared by the preparation method provided by this invention and the obtained asymmetric chiral fully conjugated carbazole pinene tetradentate platinum(II) or palladium(II) complexes have high internal and external quantum yields, luminous brightness and stability. Attached Figure Description

[0025] Figure 1 The UV-Vis absorption spectra of the palladium(II) complexes Pd-PP, Pd-PS and Pd-PO are shown. Figure 2 The emission spectra of the palladium(II) complexes Pd-PP, Pd-PS and Pd-PO are shown. Figure 3 Emission spectra (a) and broken-line plots (b) of the palladium(II) complex Pd-PP in mixed solutions of water / THF at different volume ratios; Figure 4 Emission spectra (a) and broken-line plots (b) of the palladium(II) complex Pd-PS in water / THF mixed solutions with different volume ratios; Figure 5 Emission spectra (a) and broken-line plots (b) of the palladium(II) complex Pd-PO in mixed solutions of water / THF at different volume ratios; Figure 6 This is a verification image of the compressive color change effect of the Pd-PO complex; Figure 7 Cyclic voltammetry curves for the palladium(II) complex Pd-PP; Figure 8 This is a schematic diagram of an organic electroluminescent device. Figure 9The graphs show the electroluminescence spectrum, current density-voltage-luminescence, luminescence-current efficiency, and luminescence-external quantum efficiency of the electroluminescent device. Figure 10 Electroluminescence spectra, current density-voltage-luminescence, luminescence-current efficiency, and luminescence-external quantum efficiency curves of Pd-PS at doping concentrations of 2%, 10%, 20%, and 30%. Figure 11 The graphs show the electroluminescence spectrum, current density-voltage-luminescence, luminescence-current efficiency, and luminescence-external quantum efficiency of the electroluminescent device. Figure 12 The general structural formula for phosphorescent materials composed of fully conjugated tetradentate platinum(II) or palladium(II) complexes; Figure 13 This is a diagram showing the atomic orbital occupancy ratio of three materials: Pd-PP, Pd-PS, and Pd-PO. Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1 Preparation of 1-(2-(4-bromophenyl)-2-oxoethyl)pyridine-1-iodide, a bromopyridine salt intermediate: 8.0 g (40.0 mmol) of p-bromoacetophenone and 20 mL (249 mmol) of pyridine were placed in a two-necked flask. A pyridine solution (15 mL) containing 5.1 g (20.0 mmol) of iodine was slowly added dropwise at 105 °C. After the addition was complete, the reaction was maintained at this temperature for 5 h. The mixture was then cooled to room temperature, filtered, and dried under vacuum to give 8.21 g of a bright, pale yellow solid, 1-(2-(4-bromophenyl)-2-oxoethyl)pyridine-1-iodide, with a yield of 52%.

[0028] .

[0029] Example 2 Preparation of the bromopinene ligand (6R,8R)-3-(4-bromophenyl)-pinene: The intermediates 1-(2-(4-bromophenyl)-2-oxoethyl)pyridine-1-iodide (4.1 g, 10.0 mmol), (1R)-(-)-myrtenal (1.8 g, 12.0 mmol), anhydrous ammonium acetate (1.5 g, 20.0 mmol), and dried DMF (10 mL, 130 mmol) were placed in a sealed tube. The mixture was refluxed at 150 °C for 12 h and concentrated. Water was added, and the mixture was extracted with dichloromethane (DCM). The combined organic phases were washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. Silica gel powder was added, and the mixture was rotary evaporated, dried, and concentrated to obtain the crude product. The crude product was separated by column chromatography with PE:DCM = 1:1 eluent to obtain 2.3 g of a yellow solid (6R,8R)-3-(4-bromophenyl)-pinene, with a yield of 70%. 1 H NMR (400 MHz, Chloroform-d) δ 8.23 ​​(s, 1H), 7.87(d, J = 8.6 Hz, 2H), 7.59 (d, J = 8.6 Hz, 2H), 7.51 (s, 1H), 3.04 (d, J = 2.9 Hz, 2H), 2.88 (t, J = 5.5 Hz, 1H), 2.74 (dt, J = 9.5, 5.8 Hz, 1H), 2.35 (qq, J = 5.8,3.3, 2.8 Hz, 1H), 1.45 (s, 3H), 1.26 (d, J = 9.6 Hz, 1H), 0.68 (s, 3H). .

[0030] Example 3 Preparation of nitrophenylpinene ligand (6R,8R)-3-(2'-nitro-[1,1'-biphenyl]-4-yl)-pinene: Weigh (6R,8R)-3-(4-bromophenyl)-pinene (328 mg, 1.00 mmol), o-nitrobenzoic acid (1.17 g, 7.00 mmol), tris(dibenzylacetone)dipalladium (46 mg, 0.05 mmol), cuprous iodide (114 mg, 0.60 mmol), 1,10-o-phenanthroline (180 mg, 1.00 mmol), potassium carbonate (332 mg, 2.40 mmol), 250 mg 3AMS, and NMP (10 mL, 104 mmol) solution into a sealed tube, evacuate, and react at 160 °C for 24 h. After the reaction was completed, the sample was extracted with dichloromethane, washed several times with water to remove the NMP solution, and separated by PE:DCM = 1:1 column chromatography to obtain 305 mg of yellow solid (6R,8R)-3-(2'-nitro-[1,1'-biphenyl]-4-yl)-pinene, with a yield of 82%. 1 H NMR (400 MHz, CDCl3) δ 8.23 ​​(s, 1H), 8.03 (d, J = 8.3 Hz,2H), 7.90 – 7.83 (m, 1H), 7.62 (td, J = 7.7, 1.1 Hz, 1H), 7.56 (s, 1H), 7.48(dd, J = 10.6, 4.4 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 3.04 (d, J = 2.6 Hz, 2H), 2.87 (t, J = 5.5 Hz, 1H), 2.72 (dt, J = 9.7, 5.8 Hz, 1H), 2.33 (tt, J = 5.7, 2.7Hz, 1H), 1.43 (s, 3H), 1.26 (d, J = 9.6 Hz, 1H), 0.67 (s, 3H). .

[0031] Example 4 Preparation of carbazole-based pinene ligands (6R,8R)-3-(9H-carbazole-2-yl)-pinene: (6R,8R)-3-(2'-nitro-[1,1'-biphenyl]-4-yl)-pinene (1.38 g, 3.72 mmol), triphenylphosphine (2.44 g, 9.30 mmol), and o-dichlorobenzene (5 mL, 45 mmol) were weighed into a sealed tube, and the mixture was refluxed at 190 °C for 21 h under vacuum. After the reaction was completed, the mixture was cooled to room temperature, loaded onto a wet plate, and o-dichlorobenzene and triphenylphosphine were removed with petroleum ether. The mixture was then separated by PE:EA = 4:1 column chromatography to obtain 987 mg of yellow solid (6R,8R)-3-(9H-carbazole-2-yl)-pinene, with a yield of 79%. 1 H NMR (400 MHz, DMSO-d6) δ 11.35 (s, 1H), 8.28 – 8.11 (m, 4H), 7.91 – 7.82 (m, 2H), 7.52 (d, J = 8.2 Hz, 1H), 7.45 – 7.37 (m, 1H), 7.22 – 7.14 (m, 1H), 3.12 – 2.97 (m, 2H), 2.87 (t, J = 5.4 Hz, 1H), 2.71 (dt, J = 9.4, 5.7 Hz, 1H), 2.29 (tt, J = 5.7, 2.8Hz, 1H), 1.40 (s, 3H), 1.16 (d, J = 9.5 Hz, 1H), 0.63 (s, 3H). .

[0032] Example 5 Preparation of 1-(2-(3-bromophenyl)-2-oxoethyl)pyridine-1-iodide, a bromopyridine salt intermediate: 8.0 g (40.0 mmol) of m-bromoacetophenone and 20 mL (249 mmol) of pyridine were placed in a two-necked flask. A pyridine solution (15 mL) containing 5.1 g (20.0 mmol) of iodine was slowly added dropwise at 105 °C. After the addition was complete, the reaction was maintained at this temperature for 5 h. The mixture was then cooled to room temperature, filtered, and dried under vacuum to give 8.00 g of a yellow solid, 1-(2-(3-bromophenyl)-2-oxoethyl)pyridine-1-iodide, with a yield of 51%.

[0033] .

[0034] Example 6 Preparation of the bromopinene ligand (6R,8R)-3-(3-bromophenyl)-pinene The intermediates 1-(2-(3-bromophenyl)-2-oxoethyl)pyridine-1-iodide (4.1 g, 10.0 mmol), (1R)-(-)-myrtenal (1.8 g, 12.0 mmol), anhydrous ammonium acetate (1.5 g, 20.0 mmol), and dried DMF (10 mL, 130 mmol) were placed in a sealed tube. The mixture was refluxed at 150 °C for 12 h and concentrated. Water was added, and the mixture was extracted with dichloromethane (DCM). The combined organic phases were washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. Silica gel powder was added, and the mixture was rotary evaporated, dried, and concentrated to obtain the crude product. The crude product was separated by column chromatography with PE:DCM = 1:1 eluent to obtain 2.6 g of a yellow solid (6R,8R)-3-(3-bromophenyl)-pinene, with a yield of 73%. 1 H NMR (400 MHz, CDCl3) δ 8.24 (s, 1H), 8.16 (s, 1H), 7.91 (d, J = 8.3 Hz, 1H), 7.52 (s, 2H), 7.34 (t, J = 7.9 Hz, 1H), 3.05 (s, 2H), 2.89 (t, J = 5.5 Hz, 1H), 2.81 – 2.69 (m, 1H), 2.35 (s, 1H), 1.45 (s, 3H), 1.28 (s, 1H), 0.69 (s, 3H). .

[0035] Example 7 Preparation of the pinene-based main ligand (6R,8R)-3-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)-pinene: Weigh (6R,8R)-3-(9H-carbazole-2-yl)-pinene (338 mg, 1.00 mmol), (6R,8R)-3-(3-bromophenyl)-pinene (656 mg, 2.00 mmol), cuprous iodide (191 mg, 1.00 mmol), anhydrous potassium carbonate (414 mg, 3.00 mmol), 2,2,6,6-tetramethyl-3,5-heptadecane (30 mg, 0.15 mmol), and dry DMF (10 mL, 130 mmol) into a sealed tube. Vacuum the tube and purge it with nitrogen. React at 140 °C for 36 h. After the reaction was completed, the sample was extracted with dichloromethane and separated by column chromatography with PE:EA=5:1 eluent to obtain 455 mg of yellow solid (6R,8R)-3-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)-pinene, with a yield of 78%.1 H NMR (400 MHz, DMSO-d6) δ 8.37 – 8.22 (m, 4H), 8.18 (s, 1H),8.11 (d, J = 6.2 Hz, 2H), 7.96 (d, J = 8.1 Hz, 1H), 7.86 (s, 1H), 7.78 (d, J = 6.7Hz, 2H), 7.67 (d, J = 7.7 Hz, 1H), 7.44 (t, J = 7.6 Hz, 1H), 7.36 (d, J = 8.1 Hz, 1H), 7.30 (t, J = 7.4 Hz, 1H), 2.95 (t, J = 21.1 Hz, 4H), 2.78 (dt, J = 11.3, 5.4Hz, 2H), 2.63 (s, 2H), 2.21 (s, 2H), 1.33 (s, 6H), 1.09 (d, J = 9.5 Hz, 2H), 0.55 (s, 6H). .

[0036] Example 8 Preparation of the Pt-PP complex Weigh (6R,8R)-3-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)-pinene (100 mg, 0.17 mmol), potassium tetrachloroplatinate (78 mg, 0.19 mmol), and n-butylammonium bromide (16 mg, 0.2 mmol) into a sealed tube. Evacuate the tube and purge with nitrogen. Pyrolytic acid is purged with nitrogen for 10 min. Then, 10 mL of propionic acid (134 mmol) is added to the sealed tube under nitrogen protection. The mixture is stirred at room temperature for 12 h, then heated to 120 °C and reacted for 48 h. After the reaction is complete, the reaction solution is poured into a large amount of ice water, resulting in the precipitation of a yellow solid. The solid is filtered, extracted with dichloromethane, washed with saturated brine, and separated by column chromatography using PE:DCM = 1:1 eluent to obtain 45 mg of the bright yellow product Pt-PP, with a yield of 34%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.55(s, 2H), 8.53 (d, J = 7.0 Hz, 1H), 8.43 (d,J = 6.8 Hz, 1H), 7.82-7.78 (m, 3H),7.78 (d, J = 12.8 Hz, 2H), 7.66 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.45(t, J = 8.5 Hz, 1H), 7.23-7.13 (m, 3H), 3.11 (dd, J = 6.8, 2.6 Hz, 4H), 2.92 (dt, J = 12.2, 5.0 Hz, 2H), 2.80 (dd, J = 8.6, 5.6 Hz, 2H), 2.35 (q, J = 5.3, 2.3 Hz, 2H), 1.45 (d, J = 2.8 Hz, 6H), 1.25 (d, J = 9.6 Hz, 3H), 0.84 (d, J = 3.1 Hz, 6H). .

[0037] Example 9 Preparation of the Pd-PP complex: Weigh (6R,8R)-3-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)-pinene (100 mg, 0.17 mmol), palladium acetate (43 mg, 0.19 mmol), and n-butylammonium bromide (16 mg, 0.2 mmol) into a sealed tube. Evacuate the tube and purge with nitrogen. Purge acetic acid with nitrogen for 10 min, then add 10 mL (60 mmol) of acetic acid to the sealed tube under nitrogen protection. Stir at room temperature for 12 h, then heat to 120 °C and react for 72 h. After the reaction is complete, pour the reaction solution into a large amount of ice water. A yellow solid precipitates out. Filter the solid, extract with dichloromethane, wash with saturated brine, and separate by column chromatography using PE:DCM = 1:1 eluent to obtain 27 mg of bright yellow product Pd-PP (yield 23%). 1 H NMR (400 MHz, Chloroform- d ) δ 8.31 – 8.22(m, 3H), 8.19 (s, 1H), 8.12 (d, J= 7.7 Hz, 1H), 7.89 (s, 1H), 7.78 (d, J = 12.8Hz, 2H), 7.66 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 8.5 Hz, 1H), 7.37 (t, J = 7.8 Hz, 1H), 3.12 (dd, J = 7.0, 2.8 Hz, 4H), 2.94 (dt, J = 20.7,5.4 Hz, 2H), 2.80 (ddt, J = 9.6, 8.1, 5.7 Hz, 2H), 2.38 (qt, J = 5.3, 2.3 Hz, 2H), 1.48 (d, J = 2.7 Hz, 6H), 1.27 (d, J = 10.6 Hz, 3H), 0.74 (d, J = 4.1 Hz, 6H). .

[0038] Example 10 Preparation of the aryl halogenated hydrocarbon ligand 2-(3-iodophenyl)benzo[d]thiazole: Benzothiazole (405 mg, 3.00 mmol), m-diiodobenzene (1.98 g, 6.00 mmol), silver carbonate (414 mg, 1.50 mmol), tetrakis(triphenylphosphine)palladium (116 mg, 0.10 mmol), and acetonitrile (10 mL, 192 mmol) were weighed into a foil-lined sealed tube. The tube was evacuated and purged with nitrogen, and reacted at 80 °C for 36 h. After the reaction was completed, the mixture was filtered, extracted with dichloromethane, and separated by column chromatography using PE:EA = 15:1 eluent to obtain 403 mg of a white solid 2-(3-iodophenyl)benzo[d]thiazole, with a yield of 40%. 1 H NMR (400MHz, Chloroform- d ) δ 8.49 (t, J = 1.7 Hz, 1H), 8.10 (d, J = 8.1 Hz, 1H), 8.03(ddd, J = 7.8, 1.8, 1.0 Hz, 1H), 7.93 (dd, J= 7.6, 0.8 Hz, 1H), 7.83 (ddd, J =7.8, 1.8, 1.0 Hz, 1H), 7.56 – 7.51 (m, 1H), 7.46 – 7.40 (m, 1H), 7.24 (t, J =7.8 Hz, 1H). .

[0039] Example 11 Preparation of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazol-9-yl)phenyl)benzo[d]thiazole, the main ligand of pinenethiazoles: Weigh (6R,8R)-3-(9H-carbazole-2-yl)-pinene (220 mg, 0.65 mmol), 2-(3-iodophenyl)benzo[d]thiazole (329 mg, 0.98 mmol), cuprous iodide (124 mg, 0.65 mmol), anhydrous potassium carbonate (269 mg, 1.95 mmol), L-proline (20 mg, 0.17 mmol), and dry DMF (10 mL, 130 mmol) into a sealed tube. The tube is evacuated and purged with nitrogen, and reacted at 140 °C for 36 h. After the reaction, the mixture is extracted with dichloromethane and separated by column chromatography using PE:EA = 6:1 eluent to obtain 228.5 mg of a pale yellow solid, 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]thiazole, with a yield of 64%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.38 (dt, J = 2.5, 1.1 Hz, 1H), 8.27 – 8.20 (m, 4H), 8.13 – 8.08 (m, 2H), 7.98 – 7.91 (m, 2H), 7.80 – 7.77 (m, 2H), 7.61 (s, 1H), 7.53 (ddd, J = 8.3, 7.2, 1.3 Hz, 1H), 7.49 – 7.46 (m, 2H), 7.45 – 7.40 (m, 1H),7.36 (ddd, J = 8.0, 5.4, 2.7 Hz, 1H), 3.04 (d, J = 2.8 Hz, 2H), 2.86 (t, J = 5.5Hz, 1H), 2.72 (dt, J= 9.5, 5.8 Hz, 1H), 2.32 (tt, J = 5.7, 2.8 Hz, 1H), 1.43 (s,3H), 1.26 (d, J = 9.5 Hz, 1H), 0.68 (s, 3H). .

[0040] Example 12 Preparation of the Pt-PS complex: Weigh 100 mg (0.18 mmol) of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]thiazole, 80 mg (0.2 mmol) of potassium tetrachloroplatinate, and 35 mg (0.43 mmol) of sodium acetate into a sealed tube. Evacuate the tube and purge with nitrogen. Purge acetic acid with nitrogen for 10 min, then add 10 mL (60 mmol) of acetic acid to the sealed tube under nitrogen protection. Stir at room temperature for 12 h, then heat to 120 °C and react for 72 h. After the reaction is complete, pour the reaction solution into a large amount of ice water. An orange solid precipitates out. Filter the solid, extract with dichloromethane, wash with saturated brine, and separate by column chromatography using PE:DCM = 1:1 eluent to obtain 50 mg of bright orange product Pt-PS, with a yield of 38%. 1 H NMR (400 MHz, Chloroform- d δ 8.49 (s, 1H), 8.45 (dd, J = 8.2, 5.0 Hz, 1H), 8.10 (d, J = 7.7 Hz, 2H), 7.93 (d, J = 8.1, 1H), 7.90(d, J = 7.9 Hz, 1H), 7.71 (s, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.52 – 7.47 (m, 2H),7.43 – 7.37 (m, 2H), 7.18 – 7.16 (m, 3H), 3.12 (s, 2H), 2.80 – 2.74 (m, 2H),2.35 (t, J = 5.8, 2.7 Hz, 1H), 1.42 (s, 3H), 1.32 (d, J = 8.7 Hz, 1H), 0.82 (s, 3H). .

[0041] Example 13 Preparation of the Pd-PS complex: Weigh 100 mg (0.18 mmol) of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]thiazole, 45 mg (0.20 mmol) of palladium acetate, and 50 mg (0.51 mmol) of potassium acetate into a sealed tube. Evacuate the tube and purge with nitrogen. Purge acetic acid with nitrogen for 10 min, then add 10 mL (60 mmol) of acetic acid to the sealed tube under nitrogen protection. Stir at room temperature for 12 h, then heat to 120 °C and react for 72 h. After the reaction is complete, pour the reaction solution into a large amount of ice water. An orange solid precipitates out. Filter the solid, extract with dichloromethane, wash with saturated brine, and separate by column chromatography using PE:DCM = 1:1 eluent to obtain 42 mg of bright orange product Pd-PS (35% yield). 1 H NMR (400 MHz, Chloroform- d ) δ 8.45 (s, 1H), 8.22 (dd, J = 8.2, 5.0 Hz, 2H), 8.15 (d, J = 7.7 Hz, 2H), 7.95 (dd, J = 8.1, 1.2 Hz, 1H), 7.90 (d, J = 7.9 Hz, 1H), 7.71 (s, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.61 –7.55 (m, 2H), 7.53 – 7.43 (m, 2H), 7.38 – 7.29 (m, 2H), 3.10 (s, 2H), 2.82 –2.75 (m, 2H), 2.38 (tt, J = 5.8, 2.7 Hz, 1H), 1.44 (s, 3H), 1.36 (d, J = 8.7 Hz, 1H), 0.71 (s, 3H). .

[0042] Example 14 Preparation of the aryl halogenated hydrocarbon ligand 2-(3-iodophenyl)benzo[d]oxazole Benzo[d]oxazole (357 mg, 3.00 mmol), m-diiodobenzene (1.98 g, 6.00 mmol), silver carbonate (414 mg, 1.50 mmol), tetra(triphenylphosphine)palladium (116 mg, 0.10 mmol), and acetonitrile (10 mL, 192 mmol) were weighed into a foil-lined sealed tube. The tube was evacuated and purged with nitrogen, and reacted at 80 °C for 36 h. After the reaction was completed, the mixture was filtered, extracted with dichloromethane, and separated by column chromatography using PE:EA = 15:1 eluent to obtain 196 mg of white solid 2-(3-iodophenyl)benzo[d]oxazole, with a yield of 20.4%. 1 H NMR (400MHz, Chloroform-d) δ 8.55 (s, 1H), 8.14 (d, J = 7.8 Hz, 1H), 7.81 – 7.73 (m,2H), 7.52 (dd, J = 6.0, 3.3 Hz, 1H), 7.33 (dd, J = 6.0, 3.2 Hz, 2H), 7.18 (t, J =7.9 Hz, 1H). .

[0043] Example 15 Preparation of the pineneoxazole main ligand 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]oxazole: Weigh (6R,8R)-3-(9H-carbazole-2-yl)-pinene (220 mg, 0.65 mmol), 2-(3-iodophenyl)benzo[d]oxazole (313 mg, 0.98 mmol), cuprous iodide (124 mg, 0.65 mmol), anhydrous potassium carbonate (269 mg, 1.95 mmol), 2,2,6,6-tetramethyl-3,5-heptadecane (50 mg, 0.25 mmol), and dry DMF (10 mL, 130 mmol) into a sealed tube. Vacuum the tube, purge with nitrogen, and react at 140 °C for 36 h. After the reaction was completed, the sample was extracted with dichloromethane and separated by column chromatography with PE:EA=6:1 eluent to obtain 141 mg of light yellow solid 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]oxazole, with a yield of 41%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.54 (d, J= 1.2Hz, 1H), 8.45 – 8.40 (m, 1H), 8.28 – 8.19 (m, 3H), 8.09 (d, J = 1.4 Hz, 1H), 7.94 (dd, J = 8.2, 1.5 Hz, 1H), 7.85 – 7.80 (m, 3H), 7.63 – 7.59 (m, 2H), 7.49– 7.46 (m, 2H), 7.39 (dt, J = 5.9, 3.0 Hz, 2H), 7.35 (td, J = 5.1, 2.5 Hz, 1H), 3.04 (d, J = 2.8 Hz, 2H), 2.86 (t, J = 5.5 Hz, 1H), 2.72 (dt, J = 9.5, 5.7 Hz, 1H), 2.33 (tt, J = 5.7, 2.8 Hz, 1H), 1.43 (s, 3H), 1.25 (d, J = 9.6 Hz, 1H), 0.68 (s, 3H). .

[0044] Example 16 Preparation of the Pd-PO complex: Weigh 100 mg (0.19 mmol) of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]oxazole, 47 mg (0.21 mmol) of palladium acetate, and 30 mg (0.37 mmol) of sodium acetate into a sealed tube. Evacuate the tube and purge with nitrogen. Purge acetic acid with nitrogen for 10 min, then add 10 mL (60 mmol) of acetic acid to the sealed tube under nitrogen protection. Stir at room temperature for 12 h, then heat to 120 °C and react for 72 h. After the reaction is complete, pour the reaction solution into a large amount of ice water. A yellow solid precipitates out. Filter the solid, extract with dichloromethane, wash with saturated brine, and separate by column chromatography using PE:DCM = 1:1 eluent to obtain 52 mg of bright yellow Pd-PO, with a yield of 43%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.52 (s, 1H), 8.28 (d, J = 8.2 Hz, 1H), 8.20 (d, J= 8.4 Hz, 1H), 8.12 (d, J = 7.7 Hz, 1H), 7.84 (d, J =7.9 Hz, 1H), 7.76 (d, J = 8.9 Hz, 1H), 7.68 – 7.63 (m, 3H), 7.56 (d, J = 7.9 Hz,1H), 7.52 – 7.30 (m, 5H), 3.12 (d, J = 2.8 Hz, 2H), 2.91 – 2.82 (m, 2H), 2.41(tt, J = 5.7, 2.7 Hz, 1H), 1.51 (s, 3H), 1.41 (d, J = 9.5 Hz, 1H), 0.76 (s, 3H). .

[0045] Example 17 Preparation of the aromatic heterocyclic ligand 2-(3-iodophenyl)pyridine: 2-Pyridineboronic acid (369 mg, 3.00 mmol), m-diiodobenzene (1.65 g, 5.00 mmol), potassium carbonate (691 mg, 5.00 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (74.7 mg, 0.10 mmol), and 1,4-dioxane (20 mL, 234 mmol) were weighed into a sealed tube, evacuated and purged with nitrogen, and reacted at 100 °C for 36 h. After the reaction was completed, the mixture was filtered, extracted with dichloromethane, and separated by column chromatography using PE:EA = 15:1 eluent to obtain 1.16 g of white solid 2-(3-iodophenyl)pyridine, yield 75.0%. 1 H NMR (400 MHz, Chloroform-d) δ 8.4 (d, J = 6.6 Hz, 1H), 8.16 (d, J = 7.2Hz, 1H), 7.85 (s, 1H), 7.60 (d, J = 7.4 Hz, 1H), 7.39 – 7.31 (m, 2H), 7.14 (d, J = 6.0, 1H), 6.98 (dd, J = 6.4, 3.0 Hz, 1H). .

[0046] Example 18 Preparation of the aromatic heterocyclic ligand 2-(3-bromophenyl)pyridine: Weigh 369 mg (3.00 mmol) of 2-pyridineboronic acid, 1.42 g (5.00 mmol) of m-bromoiodobenzene, 552 mg (4.00 mmol) of potassium carbonate, 116 mg (0.10 mmol) of tetra(triphenylphosphine)palladium, and 20 mL (206 mmol) of toluene into a sealed tube. The tube is then evacuated and purged with nitrogen. The reaction is carried out at 110 °C for 36 h. After the reaction is complete, the mixture is filtered, extracted with dichloromethane, and separated by column chromatography using PE:EA = 15:1 eluent to obtain 478 mg of a white solid 2-(3-bromophenyl)pyridine, with a yield of 68.7%. 1 H NMR (400 MHz, Chloroform-d)δ 8.42 (d, J = 6.8 Hz, 1H), 8.18 (d, J = 7.6 Hz, 1H), 7.90 (s, 1H), 7.61 (d, J =7.0 Hz, 1H), 7.42 – 7.37 (m, 2H), 7.16 (d, J = 6.4, 1H), 7.01 (dd, J = 6.0, 3.2Hz, 1H). .

[0047] Example 19 Preparation of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)pyridine, the main ligand of pinenepyridine: Weigh (6R,8R)-3-(9H-carbazole-2-yl)-pinene (220 mg, 0.65 mmol), 2-(3-bromophenyl)pyridine (232 mg, 1.00 mmol), cuprous iodide (124 mg, 0.65 mmol), anhydrous potassium carbonate (269 mg, 1.95 mmol), 2,2,6,6-tetramethyl-3,5-heptadecane (40 mg, 0.2 mmol), and dried DMF (10 mL, 130 mmol) into a sealed tube. The tube is evacuated and purged with nitrogen, and reacted at 140 °C for 36 h. After the reaction, the mixture is extracted with dichloromethane and separated by column chromatography using PE:EA = 6:1 eluent to obtain 256 mg of a pale yellow solid, 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)pyridine, with a yield of 52%. 1 HNMR (400 MHz, Chloroform- d) δ 8.60 (s, 1H), 8.37 (d, J = 5.9 Hz, 1H), 8.31 (s,1H), 8.20-8.12 (m, 5H), 7.80 (s, 1H), 7.66 – 7.60 (m, 2H), 7.40 – 7.31 (m,2H), 7.20 – 7.18 (m, 2H), 7.15 (d, J = 5.9 Hz, 1H), 7.01 (dd, J = 5.7, 2.9 Hz, 1H), 3.04 (d, J = 2.8 Hz, 2H), 2.86 (t, J = 5.5 Hz, 1H), 2.72 (dt, J = 9.5, 5.7 Hz, 1H), 2.33 (tt, J = 5.7, 2.8 Hz, 1H), 1.43 (s, 3H), 1.25 (d, J = 9.6 Hz, 1H), 0.68 (s, 3H). .

[0048] Example 20 Preparation of the Pd-Py complex Weigh 100 mg (0.19 mmol) of 2-(3-(2-((6S,8S)-pinene-3-yl)-9H-carbazole-9-yl)phenyl)benzo[d]oxazole, 47 mg (0.21 mmol) of palladium acetate, and 32 mg (0.33 mmol) of potassium acetate into a sealed tube. Evacuate the tube and purge with nitrogen. Purge acetic acid with nitrogen for 10 min, then add 10 mL (60 mmol) of acetic acid to the sealed tube under nitrogen protection. Stir at room temperature for 12 h, then heat to 120 °C and react for 72 h. After the reaction is complete, pour the reaction solution into a large amount of ice water. A yellow solid precipitates out. Filter the solid, extract with dichloromethane, wash with saturated brine, and separate by column chromatography using PE:DCM = 1:1 eluent to obtain 52 mg of bright yellow product Pd-PO, yield 43%. 1 H NMR (400 MHz, Chloroform- d ) δ 8.52 (s, 1H), 8.28 (d, J = 8.2 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 8.12 (d, J= 7.7 Hz, 1H), 7.84 (d, J =7.9 Hz, 1H), 7.76 (d, J = 8.9 Hz, 1H), 7.68 – 7.63 (m, 3H), 7.56 (d, J = 7.9 Hz,1H), 7.52 – 7.30 (m, 5H), 3.12 (d, J = 2.8 Hz, 2H), 2.91 – 2.82 (m, 2H), 2.41(tt, J = 5.7, 2.7 Hz, 1H), 1.51 (s, 3H), 1.41 (d, J = 9.5 Hz, 1H), 0.76 (s, 3H). . Example 21

[0049] Photophysical properties of palladium(II) complexes Pd-PP, Pd-PS and Pd-PO in dichloromethane solution: The UV-Vis absorption and emission spectra of the palladium(II) complexes Pd-PP, Pd-PS, and Pd-PO are attached. Figures 1-5 As shown. The complexes Pd-PP, Pd-PS, and Pd-PO were prepared to a concentration of 1×10⁻⁶. -4 A 2.5 mL solution of complexes Pd-PP, Pd-PS, and Pd-PO was transferred from a mol / L dichloromethane (DCM) solution into a fluorescent cuvette, and their UV-Vis absorption and emission spectra were measured. The results show that the three complexes exhibit strong absorption in the 285 nm-300 nm range, mainly due to... 1 π-π* The transition occurs, and the complex exhibits weak absorption in the 300 nm-400 nm range, primarily due to charge transfer from the singlet metal to the ligand. 1 MLCT) and spin-forbidden triplet metal-to-ligand charge transfer (MLCT) 3 MLCT). When 350nm light is used as the excitation wavelength, by Figure 2 As can be seen, the maximum emission peaks of the complexes Pt-PP, Pd-PS, and Pd-PO are at 525 nm, 536 nm, and 523 nm, respectively. Figure 3 , Figure 4 and Figure 5The results indicate that the palladium(II) complexes Pd-PP, Pd-PS, and Pd-PO exhibit aggregation-induced emission (AIE). Their emission spectra in water / THF mixed solutions with different volume ratios were tested. Since they are all insoluble in water, as the volume ratio of water in the mixed solution gradually increases, the water molecules are compressed, causing aggregation and enhancing luminescence. When the water / THF ratio reaches 90%, the solution color darkens significantly; and under 365 nm UV light irradiation, when the solution is entirely a good solvent, almost no light is emitted or only very weak light is emitted, while strong luminescence can be observed when the water ratio is 90%. Because the ligands and complexes are more widely spaced in dilute THF, and the bond twisting is relatively free, they do not emit light in dilute good solvents. However, in the aggregated state, the intermolecular forces are enhanced, and the bond twisting is restricted, resulting in stronger emission in the aggregated state. The maximum emission peaks of the complexes Pd-PP, Pd-PS, and Pd-PO in the aggregated luminescent state are approximately 594 nm, 599 nm, and 580 nm, respectively, and they also exhibit excellent stability. Among them, the Pd-PO complex shows a more pronounced piezochromic effect; after grinding, the luminescence exhibits a red shift, as shown in the attached figure. Figure 6 As shown.

[0050] Example 22 Density functional theory calculations of palladium(II) complexes Pd-PP, Pd-PS and Pd-PO: Density functional theory (DFT) calculations were performed on the complexes Pd-PP, Pd-PS, and Pd-PO using Gauss 06 to investigate the photophysical properties of these luminescent materials. The B3LYP method was used for calculations. For these three complexes, the HOMO distribution is mainly located on the electron donor carbazole ring, while the LUMO is mainly confined to the electron acceptor azole ring unit. Table 1 lists the HOMO energy levels of the three materials Pd-PP, Pd-PS, and Pd-PO as -4.59 eV, -4.82 eV, and -4.81 eV, and the LUMO energy levels as -1.44 eV, -1.82 eV, and -1.67 eV, respectively. The theoretical energy level differences for the three complexes are 3.15 eV, 3.00 eV, and 3.14 eV, respectively. The atomic orbital occupancy distribution of the three materials Pd-PP, Pd-PS, and Pd-PO is shown in the figure below. Figure 13 As shown.

[0051] Table 1

[0052]

[0053] Example 23 Electrochemical properties of palladium(II) complexes with Pd-PP, Pd-PS, and Pd-PO were tested: To investigate the HOMO and LUMO energy levels and charge carrier injection performance of palladium(II) complexes, we used cyclic voltammetry (CV) to determine the oxidation potential of the system in dichloromethane solution with Ag / AgNO3 as the reference electrode, as shown in the attached figure. Figure 7 As shown, the complexes exhibit oxidation peaks in the range of 0.73–0.82 V. Furthermore, based on the oxidation and reduction potentials of each complex, the corresponding HOMO and LUMO energy levels can be calculated, thus yielding the band gap E of the palladium(II) complexes Pd-PP, Pd-PS, and Pd-PO. g The differences between the HOMO and LUMO energy levels are 2.32 eV, 2.27 eV, and 2.33 eV, respectively.

[0054] Example 24 Fabrication of organic electroluminescent devices The device of the present invention using palladium(II) complexes Pd-PP, Pd-PS, and Pd-PO as the light-emitting layer may include: the device structure as follows Figure 8 As shown, the structure is HAT-CN (10 nm) / TAPC (30 nm) / TCTA (10 nm) / MCP: x%Pd (25 nm) / TmPyPb (35 nm) / Liq (1 nm) / Al, where HAT-CN serves as the hole injection layer; TAPC and TCTA serve as hole transport layers, also regulating energy level matching; MCP: x%Pd serves as the light-emitting layer, with MCP as the main material and doped with different concentrations of palladium(II) complexes; TmPyPb serves as the electron transport layer; Liq also regulates energy levels, and finally, Al serves as the cathode. Among the organic electroluminescent devices using Pd-PP as the light-emitting layer, the device with 30 wt% doping exhibits the best performance, with a maximum current efficiency of 20.15 cd / A, a power efficiency of 11.72 lm / W, and an external quantum efficiency of 8.26%. At 10000 cd / m², the performance is... 2 At high brightness, the device efficiencies are 13.06 cd / A, 6.03 lm / W, and 5.31%, respectively, with an EQE efficiency roll-off of 35.71%. The electroluminescence spectrum, current density-voltage-brightness, brightness-current efficiency, and brightness-external quantum efficiency curves of the electroluminescent device are attached. Figure 9 As shown. (Attached) Figure 10 Electroluminescence spectra, current density-voltage-luminescence, luminescence-current efficiency, and luminescence-external quantum efficiency curves for Pd-PS at doping concentrations of 2%, 10%, 20%, and 30%. The device exhibits the best performance, with a maximum current efficiency of 36.95 cd / A, a power efficiency of 21.50 lm / W, and an external quantum efficiency of 12.84%. At 10000 cd / m², [further details are needed]. 2At high brightness, the device efficiencies were 34.31 cd / A, 18.27 lm / W, and 12.24%, respectively, with an EQE efficiency roll-off of 4.67%. Among the organic electroluminescent devices using Pd-PO as the emitting layer, the device with 30 wt% doping exhibited the best performance, with a maximum current efficiency of 74.82 cd / A, a power efficiency of 43.53 lm / W, and an external quantum efficiency of 21.94%. Notably, at 10000 cd / m², the device achieved... 2 At high brightness, the device efficiencies are 71.92 cd / A, 38.96 lm / W, and 21.08%, respectively, with an EQE efficiency roll-off of 3.92%. The electroluminescence spectrum, current density-voltage-brightness, brightness-current efficiency, and brightness-external quantum efficiency curves of the electroluminescent device are attached. Figure 11 As shown above, the data indicates that constructing complexes with such steric hindrance in pinene structures can yield highly efficient devices.

[0055] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0056] It should be noted that the above content merely illustrates the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. For those skilled in the art, various improvements and modifications can be made without departing from the principle of the present invention, and all such improvements and modifications fall within the scope of protection of the claims of the present invention.

Claims

1. A phosphorescent material of a fully conjugated carbazole-based pinene chiral tetradentate platinum(II) or palladium(II) complex, characterized in that, The full conjugated carbazolyl pinene chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material is based on an asymmetric chiral full conjugated carbazolyl pinene tetradentate platinum (II) or palladium (II) complex phosphorescent material; the structure of the complex is shown in the following formula (I): ； Wherein, ； R1 is one of linear, branched or cyclic aliphatic alkyl, substituted alkyl, aryl, substituted aryl of 1-18 carbon atoms; R2 is one of hydrogen atom, cyano, nitro, acyl, linear, branched or cyclic aliphatic alkyl of 1-18 carbon atoms, substituted alkyl, alkoxy, aryloxy, alkylthio, arylthio, aliphatic amine group, aromatic amine group, aryl, substituted aryl.

2. The method for preparing a phosphorescent material of a fully conjugated carbazole-based pinene chiral tetradentate platinum(II) or palladium(II) complex as described in claim 1, characterized in that, It comprises the following steps: S1, the carbazolyl pinene compound shown in formula (1) and the halogenated arylbenzene substituted aromatic heterocyclic compound shown in formula (2) are dissolved in an organic solvent, and in the presence of a catalyst, a ligand and a base, reacted at 110-140 ℃ for 20-40 h to obtain a carbazolyl pinene chiral asymmetric full conjugated tetradentate ligand shown in formula (3); ； S2, the asymmetric chiral full conjugated carbazolyl pinene tetradentate ligand shown in formula (3) and potassium tetrachloroplatinate or palladium acetate are dissolved in an organic solvent, a catalyst is added, and stirred under nitrogen protection at room temperature for 6-12 h in the dark, and then heated to 120-150 ℃ for 18-72 h to obtain the asymmetric chiral full conjugated carbazolyl pinene tetradentate platinum (II) or palladium (II) complex phosphorescent material shown in formula (I); ； Wherein, X is Br or I; M is Pt or Pd; ； R1 is one of linear, branched or cyclic aliphatic alkyl, substituted alkyl, aryl, substituted aryl of 1-18 carbon atoms; R2 is one of hydrogen atom, cyano, nitro, acyl, linear, branched or cyclic aliphatic alkyl of 1-18 carbon atoms, substituted alkyl, alkoxy, aryloxy, alkylthio, arylthio, aliphatic amine group, aromatic amine group, aryl, substituted aryl.

3. The method for preparing a phosphorescent material of a fully conjugated carbazole-based pinene chiral tetradentate platinum(II) or palladium(II) complex according to claim 2, characterized in that, In step S1, the molar ratio of the compound shown in formula (1), the compound shown in formula (2), the organic solvent, the catalyst, the ligand and the base is 1:1-3:10-500:0.01-2:0.03-5:1-10.

4. A method for preparing a full-conjugated carbazolylpinene-based chiral tetradentate platinum(II) or palladium(II) complex phosphorescent material according to claim 3, characterized in that, In step S1, the catalyst is one of cuprous iodide, cuprous bromide, Pd(PPh3)4, Pd(dba)3, Pd(OAc)2; the ligand is one of 2,2,6,6-tetramethyl-3,5-heptanedione, triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, L-proline; the organic solvent is one of toluene, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane; and the base is one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, cesium carbonate, potassium trimethylsilanol.

5. The method for preparing a phosphorescent material of a fully conjugated carbazole-based pinene chiral tetradentate platinum(II) or palladium(II) complex according to claim 2, characterized in that, In step S2, the molar ratio of the asymmetric chiral full conjugated carbazolyl pinene tetradentate ligand shown in formula (3), potassium tetrachloroplatinate or palladium acetate, the organic solvent and the catalyst is 1:1-1.5:100-1000:1-5.

6. A method of preparing a full-coordinated chiral tetradentate platinum(II) or palladium(II) complex phosphorescent material of the formula of claim 5, characterized in that, In step S2, the catalyst is one of potassium acetate, sodium acetate, ammonium acetate, tetrabutylammonium bromide, and tetrabutylammonium chloride; and the organic solvent is one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetic acid, propionic acid, and butyric acid.

7. Use of a full-conjugated carbazolylpinane-based chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material according to claim 1 in an electroluminescent device.

8. Use according to claim 7, characterized in that, The full-conjugated carbazolylpinane-based chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material is used in a light-emitting layer of an electroluminescent device.

9. Use of a full-conjugated carbazolylpinane-based chiral tetradentate platinum (II) or palladium (II) complex phosphorescent material according to claim 1 in a pressure-sensing device or a pressure-sensitive device.

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