Pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes and preparation methods and applications thereof

Abstract

The invention discloses a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex and its preparation method and application, the complex is an asymmetric chiral tetradentate complex based on the pyrimidine ligand of pinene, and the general structural formula of the complex is a compound represented by the following formula (I) and formula (II): wherein R is one of N-carbazolyl, N-diphenylamine, N-phenothiazine, N-phenoxazine, N-dimethylacridinyl, 2,6-dimethyl substituted phenoxy, 2,6-diisopropyl substituted phenoxy, and hexahydropyridine. The pinene pyrimidine tetradentate platinum (II) and palladium (II) complex provided by the invention has excellent photoelectric performance, stability, film forming property, solubility and other properties, and is simple to prepare, low in cost, has aggregated luminescence and pressure-induced color performance, can be used as a light-emitting layer in electroluminescent devices, or in sensors, anti-counterfeiting, storage and display fields.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials, and specifically relates to a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex, and a preparation method and application thereof. Background Art

[0002] Heavy metal complex-based electrophosphorescent materials are the most active in current organic electroluminescence research. 6 and d 8 Heavy metal atoms with electronic structures such as platinum (Pt), iridium (Ir), and osmium (Os) have strong spin-orbit coupling, which leads to the mixing of singlet and triplet states, thus shortening the phosphorescence lifetime, increasing the intersystem crossing ability, and causing the forbidden triplet excited state to partially allow the transition to the ground state, so that phosphorescence can be emitted smoothly, improving the luminescence efficiency, and the internal quantum efficiency can reach 100%. These materials can be widely used in stress sensing, information storage, trademark anti-counterfeiting, and light-emitting devices.

[0003] At present, the research on phosphorescent metal complexes mainly focuses on iridium (III), platinum (II) and palladium (II). Among them, platinum (II) and palladium (II) complexes have square planar structures, and the ligands can be designed to be bidentate, tridentate and tetradentate. These changes will significantly affect the photophysical properties of the complexes. In particular, rigid tetradentate ligands have attracted a lot of attention because the rigid structure can suppress the vibration and rotation around the metal ions, reduce non-radiative attenuation, and have good stability. Among them, palladium (II) complexes usually show much weaker strong spin-orbit coupling effects and lack the T 1 →S 0 The effective radiation decay process of ligands. Therefore, most of them have a long decay lifetime at room temperature, which will lead to concentration quenching and seriously reduce the efficiency. However, by introducing large sterically hindered rigid groups into the structure of the ligand, the problem of concentration quenching can be effectively improved, and the luminescence efficiency can be greatly increased.

[0004] Pyrimidine-based luminescent materials are easy to synthesize and chemically modified, and have high electron affinity, luminescence efficiency, and excellent electrochemical and optical properties. Therefore, they are used in electronic devices such as OLED, OPV, OFET, and chemical biosensors. Using such dinitrogen heterocycles as ligands may synthesize electrophosphorescent materials with better performance. However, how to prepare a material with high solubility of the complex, low difficulty of coordination reaction, and high luminescence efficiency is an urgent problem to be solved. Summary of the invention

[0005] The purpose of the present invention is to develop a class of pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes with excellent photoelectric properties, stability, film-forming properties, solubility and the like, which are simple to prepare and low in cost and have aggregated luminescence and piezochromic properties, and their application in the fields of electroluminescent devices, sensors or electrochromic devices.

[0006] The present invention provides the following technical solutions:

[0007] In the first aspect, a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex is provided, wherein the complex is an asymmetric chiral tetradentate complex based on a pinene pyrimidine ligand, and the general structural formula of the complex is a compound represented by the following formula (I) and formula (II):

[0008]

[0009] Wherein, R is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylacridinyl, 2,6-dimethyl substituted phenoxy, 2,6-diisopropyl substituted phenoxy, and hexahydropyridinyl:

[0010]

[0011] In a second aspect, a method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex described in the first aspect is provided, comprising the following steps:

[0012] Under nitrogen protection, potassium tetrachloroplatinate and pinene pyrimidine ligands are dissolved in acetic acid, a catalyst is added, the reaction is carried out at room temperature in the dark, and then the temperature is raised to react to obtain a pinene pyrimidine tetradentate platinum (II) complex as shown in formula (I);

[0013] Under nitrogen protection, palladium acetate and pinene pyrimidine ligands are dissolved in acetic acid, a catalyst is added, and the reaction is carried out at room temperature in the dark, and then the temperature is raised to react to obtain a pinene pyrimidine tetradentate palladium (II) complex as shown in formula (II).

[0014] Furthermore, the molar ratio of the raw materials used to prepare the pinene pyrimidine tetradentate platinum (II) complex is: potassium tetrachloroplatinate: catalyst: pinene pyrimidine ligand: acetic acid = 1.0-1.5: 1-5: 1: 100-500.

[0015] Furthermore, the molar ratio of the raw materials used to prepare the pinene pyrimidine tetradentate palladium (II) complex is: palladium acetate: catalyst: pinene pyrimidine ligand: acetic acid = 1.0-1.5: 1-5: 1: 100-500.

[0016] Furthermore, the catalyst is one of potassium acetate, sodium acetate and ammonium acetate.

[0017] Furthermore, the preparation method of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex specifically comprises the following steps:

[0018]

[0019] Dissolve dichloropyrimidine and 3-methoxyphenylboronic acid in a mixed solution of an organic solvent and water in the presence of a palladium catalyst and a base, and reflux for 20 to 30 hours to obtain a methoxypyrimidine derivative as shown in formula (1-1);

[0020] The methoxypyrimidine derivative is dissolved in an organic solvent, a compound with an active group is added, and the mixture is reacted at 20 to 50° C. for 10 to 20 hours in the presence of a base to obtain a pyrimidine derivative as shown in formula (1-2);

[0021] The pyrimidine derivative is dissolved in an acid and refluxed for 40 to 50 hours to obtain a hydroxypyrimidine derivative as shown in formula (1);

[0022] Dissolve m-bromoacetophenone in pyridine as a raw material, add iodine pyridine solution, and react at 100-120°C for 5-10 hours to obtain a pyridinium salt derivative as shown in formula (2-1);

[0023] The pyridinium salt derivative, enal derivative and organic salt are dissolved in an organic solvent and refluxed for 10 to 20 hours to obtain a bromopinene derivative as shown in formula (2);

[0024] The hydroxypyrimidine derivatives shown in formula (1) and the bromopinene derivatives shown in formula (2) are dissolved in an organic solvent, and reacted at 100 to 130° C. for 20 to 40 hours in the presence of cuprous iodide and a base to obtain a pinene pyrimidine chiral asymmetric tetradentate ligand shown in formula (3);

[0025] Under nitrogen protection, a pinene pyrimidine chiral asymmetric tetradentate ligand as shown in formula (3) and potassium tetrachloroplatinate are dissolved in acetic acid, a catalyst is added, and the mixture is stirred at room temperature in the dark for 6 to 12 hours, and then the temperature is raised to 120 to 150° C. for reaction for 18 to 72 hours to obtain a pinene pyrimidine tetradentate palladium (II) complex as shown in formula (I);

[0026] Under nitrogen protection, the pinene pyrimidine chiral asymmetric tetradentate ligand and palladium acetate as shown in formula (3) are dissolved in glacial acetic acid, a catalyst is added, and the mixture is stirred at room temperature in the dark for 6 to 12 hours, and then the temperature is raised to 120 to 150° C. and reacted for 18 to 72 hours to obtain the pinene pyrimidine tetradentate palladium (II) complex as shown in formula (II).

[0027] Furthermore, the raw materials for preparing the methoxypyrimidine derivatives as shown in formula (1-1) are calculated by molar parts: 1 part of dichloropyrimidine, 1-1.5 parts of 3-methoxyphenylboric acid, 0.03-0.05 parts of palladium catalyst, 3-5 parts of base, 10-50 parts of polar organic solvent, and 5-25 parts of water; the palladium catalyst is one of tetrakistriphenylphosphine palladium, bis(triphenylphosphine)palladium dichloride, and 1,1'-bis(diphenylphosphino)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, NN, dimethylformamide, tetrahydrofuran, and 1,4-dioxane.

[0028] Furthermore, the raw materials for preparing the pyrimidine derivatives shown in formula (1-2) are calculated by molar parts: 1 part of methoxy pyrimidine derivatives, 10 to 50 parts of organic solvents, 1 to 2 parts of compounds with active groups, and 3 to 10 parts of bases; the organic solvent is one of toluene, N,N-dimethylformamide, tetrahydrofuran, and 1,4-dioxane; the base is one of sodium hydride and n-butyl lithium; R in formula (1-2) is one of N-carbazolyl, N-diphenylamine, N-phenothiazine, N-phenoxazine, N-dimethylacridinyl, 2,6-dimethyl substituted phenoxy, 2,6-diisopropyl substituted phenoxy, and hexahydropyridine.

[0029] Furthermore, the raw materials for preparing the hydroxypyrimidine derivatives as shown in formula (1) are calculated by molar proportions as follows: 1 part of the compound shown in formula (1-2) and 40 to 100 parts of an acid; the acid is one of hydrobromic acid and acetic acid.

[0030] Furthermore, the raw materials for preparing the pyridinium salt derivatives as shown in formula (2-1) are calculated by molar proportions as follows: 1 part of m-bromoacetophenone, 10 to 50 parts of pyridine, and 0.5 to 1 part of iodine.

[0031] Furthermore, the raw materials for preparing the brominated pinene derivatives as shown in formula (2) are calculated by molar proportions as follows: 1 part of a pyridinium salt derivative, 1 to 1.5 parts of an aldehyde derivative, 2 to 3 parts of an organic salt, and 10 to 50 parts of an organic solvent; the organic salt is one of ammonium acetate, sodium acetate, and potassium acetate; the organic solvent is one of toluene, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, methanol, ethanol, and dimethyl sulfoxide.

[0032] Furthermore, the molar ratio of the raw materials used to prepare the pinene pyrimidine chiral asymmetric tetradentate ligand shown in formula (3) is: hydroxypyrimidine derivative shown in formula (1): bromopinene derivative shown in formula (2): organic solvent: cuprous iodide: base = 1:1:10-50:0.01-0.1:1-10; the organic solvent is one of toluene, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane; the base is one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, potassium phosphate, and cesium carbonate.

[0033] In a third aspect, there is provided an application of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex described in the first aspect, which is applied as a light-emitting layer in an electroluminescent device, or in the fields of sensors, anti-counterfeiting, storage and display.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The present invention applies a pinene pyrimidine compound with a stereoscopic structure to a tetradentate platinum (II) and palladium (II) complex, and obtains a tetradentate platinum (II) and palladium (II) complex phosphorescent material with a huge spatial steric hindrance structure by introducing different substituents. Such tetradentate platinum (II) and palladium (II) complex phosphorescent material has a strong aggregated luminescence performance. When applied to the light-emitting layer of an organic electroluminescent device, the large spatial steric hindrance of the pinene structure can effectively inhibit the concentration quenching caused by the aggregation of molecules. The saturated alicyclic structure effectively regulates the solubility of the complex, thereby realizing an efficient phosphorescent device. At the same time, the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex phosphorescent material can change the stacking structure of molecules through external forces to achieve a change in luminescent color due to the introduction of a freely rotatable substituent. Such a material has good pressure-induced color-changing properties and can be potentially used in the fields of data recording, data storage, pressure sensor devices and pressure-sensitive devices.

[0036] (2) The present invention achieves aggregation-induced luminescence effect by introducing a large sterically hindered pinene structure containing a saturated aliphatic ring that wraps the platinum and palladium cores, an electron-deficient pyrimidine unit and different electron-donating structures on the ligand, effectively suppresses the concentration quenching effect caused by long lifetime, improves the luminescence efficiency of the platinum and palladium (II) complex phosphorescent materials to the greatest extent, and also achieves a piezochromic effect; in the present invention, the halogen atoms are replaced by compounds containing active groups to further improve the solubility, hole transport ability and thermal stability of the complex. In addition, the introduction of these groups can produce a certain spatial effect, thereby reducing the interaction between the luminescence centers of the complex, reducing the self-quenching phenomenon of triplet excitons, and improving the luminescence performance of the material.

[0037] (3) The pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes provided by the present invention have a simple synthesis method and are easy to purify. The electroluminescent device prepared by the pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes provided by the present invention has high internal and external quantum yields, luminescence brightness and stability. In addition, since the pinene pyrimidine tetradentate platinum (II) and palladium (II) complexes have significant aggregated luminescence properties and piezochromic properties, they can also be used in sensors, anti-counterfeiting, storage and display fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is the ultraviolet absorption (UV) spectra of the phosphorescent platinum (II) complex Pt-MDP and the palladium (II) complexes Pd-MD and Pd-MDP in dichloromethane in Example 22;

[0039] Figure 2 is the fluorescence emission (PL) spectrum of the phosphorescent platinum (II) complex Pt-MDP in dichloromethane in Example 22;

[0040] Figure 3 : The emission (PL) spectra of the phosphorescent palladium (II) complex Pd-MD in water / tetrahydrofuran (THF) mixtures with different water content ratios in Example 22 (the percentages in the figure refer to the volume percentage of water in the water / tetrahydrofuran mixture);

[0041] Figure 4 : The emission (PL) spectra of the phosphorescent palladium (II) complex Pd-MDP in water / tetrahydrofuran (THF) mixtures with different water content ratios in Example 22 (the percentages in the figure refer to the volume percentage of water in the water / tetrahydrofuran mixture);

[0042] Figure 5 The piezochromic effect of the phosphorescent palladium (II) complex Pd-MDP in Example 22;

[0043] Figure 6 Density functional theory calculations for the phosphorescent platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in Example 23;

[0044] Figure 7 cyclic voltammetry (CV) curves of the phosphorescent platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP in dichloromethane solution in Example 24;

[0045] Figure 8 is the device structure diagram and the molecular structure formula of other materials used in the device in Example 25;

[0046] Fig. 9The electroluminescence spectra (a), current density-voltage-brightness (b), brightness-current efficiency (c) and brightness-external quantum efficiency (d) of the electroluminescent device based on the phosphorescent palladium (II) complex Pd-MD at doping concentrations of 5%, 10%, 15%, 20% and 100% in Example 25 are graphs;

[0047] Fig.10 The electroluminescence spectra (a), current density-voltage-brightness (b), brightness-current efficiency (c) and brightness-external quantum efficiency (d) curves of the electroluminescent device based on the phosphorescent palladium (II) complex Pd-MDP at doping concentrations of 5%, 10%, 15%, 20% and 100% in Example 25. DETAILED DESCRIPTION

[0048] The present invention discloses a pinene pyrimidine tetradentate platinum (II) and palladium (II) complex and a preparation method and application thereof, wherein the tetradentate platinum (II) and palladium (II) complex modified by pinene and pyrimidine is connected by oxygen atoms. The tetradentate phosphorescent platinum and palladium (II) complex of the present invention achieves an aggregation-induced luminescence effect by introducing a large sterically hindered pinene structure containing a saturated aliphatic ring that wraps the platinum and palladium cores, an electron-deficient pyrimidine unit and different electron-donating structures on the ligand, effectively suppresses the concentration quenching effect caused by the long life, improves the luminescence efficiency of the phosphorescent material of the platinum and palladium (II) complex to the greatest extent, and also achieves a pressure-induced color change effect. The preparation method and the obtained pinene-based pyrimidine tetradentate platinum (II) and palladium (II) complex have high internal and external quantum yields, luminescence brightness and stability. The electroluminescent device of the present invention has a light-emitting layer, which is a pyrimidine tetradentate platinum (II) and palladium (II) complex based on pinene, and is prepared by a vapor deposition film-making method under specific conditions. It has low cost, simple operation, stable chemical properties, high luminous brightness and efficiency, and is helpful to realize a high-efficiency electroluminescent device.

[0049] In order to better understand the content of the present invention, the technical scheme of the present invention is further described below through specific examples and illustrations, including synthesis, property determination, titration experiment, etc. These implementation examples are only for the purpose of explaining the present invention and do not limit the present invention.

[0050] Example 1

[0051] Preparation of methoxypyrimidine intermediate 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PYP.

[0052] Weigh 3,6-dichloropyrimidine (8.9 g, 60 mmol), 3-methoxyphenylboronic acid (10.9 g, 72 mmol), tetrakistriphenylphosphine palladium (2.4 g, 1.6 mmol), tetrabutylammonium bromide (1.9 g, 6 mmol) and potassium carbonate (24.8 g, 180 mmol) in a round-bottom flask, evacuate and fill with nitrogen three times, inject water (25 mL, 1388 mmol) and toluene (75 mL, 706 mmol) under nitrogen protection, and reflux at 120°C for 24 h. After the reaction is completed, cool to room temperature, extract with dichloromethane, collect the organic layer, dry, concentrate, and use V PE :V EA =20:1 column chromatography separation to obtain 8 g of white solid 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PP with a yield of 68.2%. 1 HNMR (400MHz, CDCl 3 )δ9.03(s,1H),7.73(s,1H),7.68–7.64(m,1H),7.61(d,J=8.2Hz,1H),7.43(t,J=8.0Hz,1H),7.09(d,J=8.2Hz,1H),3.90(s,3H).

[0053]

[0054] Example 2

[0055] Preparation of pyrimidine intermediate 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-10H-phenoxazine M-PYP.

[0056] Weigh phenoxazine (4.6 g, 25 mmol) and put it into a reaction bottle. Vacuum and replace nitrogen 3-5 times. Place the reaction in an ice bath at 0°C. Add tetrahydrofuran (40 mL, 494 mmol) under nitrogen protection. At 0°C, drop 2.5 mol / L n-butyl lithium (11.3 mL, 28.9 mmol) into the reaction bottle. After 1 hour, drop 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PYP (5.5 g, 25 mmol) in dry tetrahydrofuran solution into the reaction bottle. After the addition is complete, allow the reaction to warm to room temperature naturally and stir overnight at room temperature. Add saturated ammonium chloride solution to quench the reaction, extract with dichloromethane, dry, concentrate, and use V PE :V EA =20:1 column chromatography separation to obtain 6.2 g of light yellow solid 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-10H-phenoxazine M-PYP with a yield of 70.6%. 1 H NMR (400 MHz, CDCl 3)δ8.91(s,1H),7.80(d,J=7.0Hz,2H),7.53(d,J=9.9Hz,2H),7.45(d,J=8.6Hz,1H) ,7.38(t,J=7.9Hz,1H),7.20(d,J=21.7Hz,6H),7.03(d,J=7.8Hz,1H),3.90(s,3H).

[0057]

[0058] Example 3

[0059] Preparation of hydroxypyrimidine ligand 3-(6-(10H-benzoxazin-10-yl)pyrimidin-4-yl)phenol OH-PYP.

[0060] Weigh 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-10H-phenoxazine M-PYP (5 g, 13.6 mmol) into a round-bottom flask, inject hydrobromic acid (30 mL, 1084 mmol) and glacial acetic acid (100 mL, 890 mmol), and reflux at 120°C for 2 days. After the reaction is completed, cool to room temperature, add a large amount of ice water to the reaction solution, and a yellow-brown solid precipitates, which is filtered. Use V PE :V EA =3:1 column chromatography separation to obtain 3.4 g of yellow solid 3-(6-(10H-benzoxazin-10-yl)pyrimidin-4-yl)phenol OH-PYP with a yield of 71.4%. 1 HNMR (400MHz, DMSO) δ9.71 (s, 1H), 8.86 (s, 1H), 7.82 (d, J = 7.7Hz, 2H), 7.51 (s, 1H), 7.44–7.35 (m, 2H), 7.32–7.21 (m, 7H), 6.91 (d, J = 7.9Hz, 1H).

[0061]

[0062] Example 4

[0063] Preparation of brominated pinene ligand (6R,8R)-3-(3-bromophenyl)-pinene Br-DPTM.

[0064] Place m-bromoacetophenone (8.0 g, 40.0 mmol) and pyridine (40 mL, 497 mmol) in a three-necked flask, and slowly drop iodine (5.1 g, 20.0 mmol) in pyridine at 105°C. After the dropwise addition, keep warm for 5 h, cool to room temperature, filter, and vacuum dry to obtain 14.0 g of yellow solid 1-(2-(3-bromophenyl)-2-oxoethyl)pyridin-1-ium iodide Br-OPPI, with a yield of 87.9%. Place the above product Br-OPPI (4.1 g, 10.0 mmol), (1R)-(-)-myrtolide aldehyde (1.8 g, 12.0 mmol), anhydrous ammonium acetate (1.5 g, 20.0 mmol), and DMF (10 mL, 130 mmol) in a single-necked flask. React at 120°C for 12 h, and concentrate. Add water, extract with dichloromethane, wash the combined organic phases with water, wash with saturated brine, dry over anhydrous sodium sulfate, filter and concentrate to obtain a crude product, separate by column chromatography to obtain 2.3 g of yellow powder (6R, 8R)-3-(3-bromophenyl)-pinene Br-DPTM, with a yield of 70.0%. 1 H NMR (400 MHz, CDCl 3 )δ8.24(s,1H),8.16(s,1H),7.91(d,J=8.3Hz,1H),7.52(s,2H),7.34(t,J=7.9Hz,1H),3.05(s,2 H), 2.89 (t, J = 5.5Hz, 1H), 2.81–2.69 (m, 1H), 2.35 (s, 1H), 1.45 (s, 3H), 1.28 (s, 1H), 0.69 (s, 3H).

[0065]

[0066] Example 5

[0067] Preparation of pinene pyrimidine primary ligand pinene phenoxy pyrimidine-10H-phenoxazine DTMP.

[0068] Weigh (6R, 8R)-3-(3-bromophenyl)-pinene Br-DPTM (327.0 mg, 1.0 mmol), 3-(6-(10H-phenoxazine-10-yl)pyrimidin-3-yl)phenol OH-PYP (353.0 mg, 1.0 mmol), CuI (19.0 mg, 0.1 mmol), cesium carbonate (977.0 mg, 3.0 mmol), 2-pyridinecarboxylic acid (0.3 g, 2.0 mmol) and place in a sealed tube, add 5 mL of DMSO (5 mL, 50 mmol) after nitrogen gas deoxygenation, evacuate and fill with nitrogen three times, and react at 120°C for 24 h. After the reaction is completed, extract with dichloromethane, dry with anhydrous sodium sulfate, and separate by developing agent column chromatography to obtain yellow powder pinene phenoxypyrimidine-10H-phenoxazine DTMP 0.3 g, with a yield of 50%. 1 H NMR (400MHz, DMSO) δ8.83(s,1H),8.18(s,1H),7.90(d,J=8.0Hz,1H),7.75(d,J=9.9Hz,4H),7.63(s,1H),7.52(d,J=15.5Hz,3 H),7.20(dd,J=19.7,11.6Hz,9H),2.99(s,2H),2.86(s,1H),2.68(s,1H),2.29(s,1H),1.39(s,3H),1.14(s,1H),0.59(s,3H).

[0069]

[0070] Example 6

[0071] Preparation of complex Pd-MD.

[0072] Weigh pinene phenoxy pyrimidine-10H-phenoxazine DTMP (120.0 mg, 0.2 mmol), Pd(OAc) 2 (42.0mg, 0.22mmol), TBAB (8.0mg, 0.1mmol) were placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10min, acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12h, and then heated to 120℃ for 72h. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and a yellow solid was precipitated, which was filtered. V PE :V DCM =2:1 developing solvent for column chromatography separation to obtain 58.0 mg of bright yellow powder Pd-MD with a yield of 43.0%. 1 H NMR (400 MHz, CDCl 3)δ8.94(s,1H),8.18(s,1H),7.83(s,2H),7.74(s,1H),7.65(s,1H),7.48(s,1H),7.34–7.27(m,5H),7.21(d,J=9.5Hz, 6H), 3.10 (s, 2H), 2.99 (s, 1H), 2.79 (s, 1H), 2.38 (s, 1H), 2.22 (t, J = 7.6Hz, 1H), 2.01 (s, 1H), 1.48 (s, 3H), 0.71 (s, 3H).

[0073]

[0074] Example 7

[0075] Preparation of pyrimidine intermediate 9-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9H-carbazole M-PYC.

[0076] Weigh carbazole (4.2g, 25mmol) and put it into the reaction bottle. Vacuum and replace nitrogen 3-5 times. Place the reaction in a 0℃ ice bath. Under nitrogen protection, add tetrahydrofuran (40mL, 494mmol). At 0℃, add 2.5 mol / L n-butyl lithium (11.3mL, 28.9mmol) to the reaction bottle. After 1h, add 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PYP (5.5g, 25mmol) in dry tetrahydrofuran solution to the reaction bottle. After the addition is complete, allow the reaction to warm to room temperature naturally and stir at room temperature overnight. Add saturated ammonium chloride solution to quench the reaction, extract with dichloromethane, dry, concentrate, and use V PE :V EA =20:1 column chromatography separation to obtain 5.3 g of light yellow solid 9-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9H-carbazole M-PYC with a yield of 60.8%. 1 H NMR (400 MHz, CDCl 3 )δ9.12(d,J=1.5Hz,1H),8.21–8.13(m,2H),7.67–7.59(m,3H),7.55–7.48 (m,2H),7.40–7.27(m,5H),6.93(ddd,J=8.0,2.2,1.2Hz,1H),3.83(s,3H).

[0077]

[0078] Example 8

[0079] Preparation of hydroxypyrimidine ligand 3-(6-(9H-carbazol-9-yl)pyrimidin-4-yl)phenol OH-PYC.

[0080] Weigh 9-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9H-carbazole M-PYC (5 g, 14.2 mmol) in a round-bottom flask, inject hydrobromic acid (30 mL, 1084 mmol) and glacial acetic acid (100 mL, 890 mmol), and reflux at 120°C for 2 days. After the reaction is completed, cool to room temperature, add a large amount of ice water to the reaction solution, and a yellow-brown solid precipitates, which is filtered. Use V PE :V EA =3:1 column chromatography separation to obtain 3.9 g of yellow solid 3-(6-(9H-carbazol-9-yl)pyrimidin-4-yl)phenol OH-PYC with a yield of 81.7%. 1 H NMR (400 MHz, CDCl 3 )δ9.12(d,J=1.5Hz,1H),8.77(s,1H),8.21–8.13(m,2H),7.66–7.59(m,2H),7.55–7.45(m,2H),7.37( ddd,J=7.4,6.2,1.3Hz,1H),7.33–7.28(m,3H),7.28–7.22(m,2H),6.81(ddd,J=8.2,2.2,1.1Hz,1H).

[0081]

[0082] Example 9

[0083] Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-carbazole CPDT.

[0084] Weigh (6R, 8R)-3-(3-bromophenyl)-pinene Br-DPTM (327.0 mg, 1.0 mmol), 3-(6-(9H-carbazole-9-yl)pyrimidin-4-yl)phenol OH-PYC (339.0 mg, 1.0 mmol), CuI (19.0 mg, 0.1 mmol), cesium carbonate (977.0 mg, 3.0 mmol), 2-pyridinecarboxylic acid (0.3 g, 2.0 mmol) and place in a sealed tube, add 5 mL of DMSO (5 mL, 50 mmol) after nitrogen bubbling and deoxygenation, evacuate and fill with nitrogen three times, and react at 120°C for 24 hours. After the reaction is completed, extract with dichloromethane, dry with anhydrous sodium sulfate, and separate by developing agent column chromatography to obtain 0.34 g of yellow powder pinene phenoxy pyrimidine-10H-carbazole CPDT, with a yield of 57.2%. 1 H NMR (400 MHz, CDCl 3)δ9.12(d,J=1.4Hz,1H),8.20–8.14(m,2H),7.72(ddd,J=8.6,2.3,1.2Hz,1H),7.66–7.59(m,3H),7.55–7.40(m,5H),7.40–7.30(m,5H) ,7.04(ddd,J=7.8,2.2,1.2Hz,2H),3.21–3.08(m,2H),3.08–2.99(m,1H),2.31–2.19(m,1H),2.00–1.90(m,2H),0.97(d,J=16.5Hz,6H).

[0085]

[0086] Example 10

[0087] Preparation of complex Pt-CD.

[0088] Weigh the main ligand pinene phenoxy pyrimidine-10H-carbazole CPDT (117.2 mg, 0.2 mmol), K 2 PtCl 4 (92.0mg, 0.22mmol) was placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10 minutes, and acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12 hours, and then heated to 120℃ for 72 hours. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and a red solid precipitated, which was filtered. PE :V DCM =2:1 developing solvent for column chromatography separation to obtain 32.8 mg of red powder Pt-DA with a yield of 21%. 1 H NMR (400 MHz, CDCl 3 )δ9.05(d,J=0.8Hz,1H),8.20–8.14(m,2H),7.66–7.60(m,2H),7.48(d,J=5.7Hz,3H),7.40–7.27(m,6H),6.91–6.85(m,1H),6.73(ddd,J=18 .5,7.7,1.3Hz,2H),6.60(dd,J=7.7,1.3Hz,1H),3.11–2.90(m,3H),2.01–1.87(m,2H),1.78(dt,J=12.0,7.8Hz,1H),0.97(d,J=16.5Hz,6H).

[0089]

[0090] Embodiment 11

[0091] Preparation of complex Pd-CD.

[0092] Weigh the main ligand pinene phenoxy pyrimidine-10H-carbazole CPDT (117.2 mg, 0.2 mmol), Pd(OAc) 2 (42.0mg, 0.22mmol), TBAB (8.0mg, 0.1mmol) were placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10min, acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12h, and then heated to 120℃ for 72h. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and an orange-red solid precipitated, which was filtered. V PE :V DCM =2:1 developing solvent for column chromatography separation to obtain 28.3 mg of bright orange powder Pd-DA with a yield of 20.5%. 1 H NMR (400 MHz, CDCl 3 )δ8.87(d,J=0.8Hz,2H),8.20–8.14(m,4H),7.82(dd,J=8.2,1.4Hz,2H),7.66–7.60(m,4H),7.56–7.48(m,6H),7.44–7.28(m,15H),7.27(d,J =1.0Hz,1H),6.67(ddd,J=20.6,7.9,1.2Hz,4H),3.11–2.91(m,6H),2.01–1.87(m,4H),1.78(dt,J=12.1,7.8Hz,2H),0.97(d,J=16.5Hz,12H).

[0093]

[0094] Example 12

[0095] Preparation of pyrimidine intermediate 6-(3-methoxyphenyl)-N,N-diphenylpyrimidin-4-amine M-NDA.

[0096] Weigh diphenylamine (4.2 g, 25 mmol) and put it into the reaction bottle. Vacuum and replace nitrogen 3-5 times. Place the reaction in an ice bath at 0°C. Add tetrahydrofuran (40 mL, 494 mmol) under nitrogen protection. At 0°C, drop 2.5 mol / L n-butyl lithium (11.3 mL, 28.9 mmol) into the reaction bottle. After 1 hour, drop 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PYP (5.5 g, 25 mmol) in dry tetrahydrofuran solution into the reaction bottle. After the addition is complete, allow the reaction to warm to room temperature naturally and stir overnight at room temperature. Add saturated ammonium chloride solution to quench the reaction, extract with dichloromethane, dry, concentrate, and use V PE:V EA =20:1 column chromatography separation to obtain 5.7 g of light yellow solid 6-(3-methoxyphenyl)-N,N-diphenylpyrimidin-4-amine M-NDA with a yield of 65.4%. 1 H NMR (400 MHz, CDCl 3 )δ8.50(d,J=1.5Hz,1H),7.64(ddd,J=8.8,2.3,1.2Hz,1H),7.52(t,J=2.2Hz,1H),7.36(dd,J=8.7,7.9Hz,1H),7.29(tt,J=7.6,1 .6Hz, 4H), 7.20 (d, J=1.4Hz, 1H), 7.17–7.10 (m, 4H), 7.04 (tt, J=7.8, 1.5Hz, 2H), 6.93 (ddd, J=8.0, 2.2, 1.2Hz, 1H), 3.83 (s, 3H).

[0097]

[0098] Example 13

[0099] Preparation of hydroxypyrimidine ligand 3-(6-(diphenylamino)pyrimidin-4-yl)phenol OH-NDA.

[0100] Weigh 6-(3-methoxyphenyl)-N,N-diphenylpyrimidine-4-amine M-NDA (5g, 14.2mmol) in a round-bottom flask, inject hydrobromic acid (30mL, 1084mmol) and glacial acetic acid (100mL, 890mmol), and reflux at 120℃ for 2 days. After the reaction is completed, cool to room temperature, add a large amount of ice water to the reaction solution, and a yellow-brown solid precipitates, which is filtered. Use V PE :V EA =3:1 column chromatography separation to obtain 4.4 g of yellow solid 3-(6-(diphenylamino)pyrimidin-4-yl)phenol OH-NDA with a yield of 92.5%. 1 H NMR (400 MHz, CDCl 3 )δ8.77(s,1H),8.51(d,J=1.5Hz,1H),7.48(ddd,J=8.4,2.2,1.2Hz,1H),7.33–7.23(m,6H),7.20( d,J=1.5Hz,1H),7.17–7.10(m,4H),7.04(tt,J=7.9,1.5Hz,2H),6.81(ddd,J=8.2,2.2,1.1Hz,1H).

[0101]

[0102] Embodiment 14

[0103] Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-diphenylamine DPNA.

[0104] Weigh (6R, 8R)-3-(3-bromophenyl)-pinene Br-DPTM (327.0 mg, 1.0 mmol), 3-(6-(diphenylamino)pyrimidin-4-yl)phenol OH-NDA (339.0 mg, 1.0 mmol), CuI (19.0 mg, 0.1 mmol), cesium carbonate (977.0 mg, 3.0 mmol), 2-pyridinecarboxylic acid (0.3 g, 2.0 mmol) and place in a sealed tube, add 5 mL of DMSO (5 mL, 50 mmol) after nitrogen bubbling and deoxygenation, evacuate and fill with nitrogen three times, and react at 120°C for 24 hours. After the reaction is completed, extract with dichloromethane, dry with anhydrous sodium sulfate, and separate by developing agent column chromatography to obtain yellow powder pinene phenoxypyrimidine-10H-diphenylamine DPNA 0.4 g, with a yield of 68.3%. 1 HNMR (400MHz, CDCl 3 )δ8.50(d,J=1.5Hz,1H),8.22(s,1H),7.72(ddd,J=8.6,2.3,1.2Hz,1H),7.63(ddd,J= 8.6,2.2,1.1Hz,1H),7.53–7.48(m,2H),7.48–7.37(m,3H),7.33–7.26(m,4H),7.20(d, J=1.4Hz,1H),7.17–7.10(m,4H),7.04(dddd,J=7.8,5.8,3.6,1.5Hz,4H),3.21–3.08(m ,2H),3.08–2.99(m,1H),2.31–2.19(m,1H),2.02–1.90(m,2H),0.97(d,J=16.5Hz,6H).

[0105]

[0106] Embodiment 15

[0107] Preparation of complex Pt-PN.

[0108] Weigh the main ligand pinene phenoxy pyrimidine-10H-diphenylamine DPNA (117.2 mg, 0.2 mmol), K 2 PtCl 4(92.0mg, 0.22mmol) was placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10 minutes, and acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12 hours, and then heated to 120℃ for 72 hours. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and a red solid precipitated, which was filtered. PE :V DCM =2:1 developing solvent for column chromatography separation to obtain red powder Pt-PN32.8 mg, with a yield of 21%. 1 H NMR (400 MHz, CDCl 3 )δ9.05(d,J=0.8Hz,1H),7.48(d,J=5.6Hz,2H),7.42(s,1H),7.40–7.26( m,6H),7.17–7.10(m,4H),7.04(tt,J=7.7,1.5Hz,2H),6.91–6.85(m,1H), 6.73(ddd,J=18.5,7.7,1.3Hz,2H),6.64–6.59(m,1H),3.11–2.90(m,3H) ,2.01–1.87(m,2H),1.78(dt,J=12.1,7.8Hz,1H),0.97(d,J=16.5Hz,6H).

[0109]

[0110] Example 16

[0111] Preparation of complex Pd-PN.

[0112] Weigh the main ligand pinene phenoxy pyrimidine-10H-diphenylamine DPNA (117.2 mg, 0.2 mmol), Pd(OAc) 2 (42.0mg, 0.22mmol), TBAB (8.0mg, 0.1mmol) were placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10min, acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12h, and then heated to 120℃ for 72h. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and an orange-red solid precipitated, which was filtered. V PE :V DCM =2:1 developing solvent for column chromatography separation to obtain 35.0 mg of bright orange powder Pd-DA with a yield of 25.3%. 1 H NMR (400 MHz, CDCl 3)δ9.59(s,1H),8.87(d,J=0.8Hz,1H),7.82(dd,J=8.2,1.4Hz,1H),7.56–7.50(m,2H ),7.44(s,1H),7.38(s,1H),7.33–7.25(m,7H),7.17–7.10(m,4H),7.04(tt,J=7.7,1 .5Hz,2H),6.67(ddd,J=20.5,7.9,1.2Hz,2H),3.07(dd,J=12.4,4.5Hz,1H),3.03–2 .91(m,2H),2.02–1.87(m,2H),1.78(dt,J=12.0,7.8Hz,1H),0.97(d,J=16.5Hz,6H).

[0113]

[0114] Embodiment 17

[0115] Preparation of pyrimidine intermediate 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9,9-dimethyl-9,10-dihydroacridine M-PDD.

[0116] Weigh 9,10-dihydro-9,9-dimethylacridine (5.2 g, 25 mmol) and put it into a reaction bottle. Vacuum and replace nitrogen 3-5 times. Place the reaction in an ice bath at 0°C. Add tetrahydrofuran (40 mL, 494 mmol) under nitrogen protection. At 0°C, drop 2.5 mol / L n-butyl lithium (11.3 mL, 28.9 mmol) into the reaction bottle. After 1 hour, drop 4-chloro-6-(3-methoxyphenyl)pyrimidine ClM-PYP (5.5 g, 25 mmol) in dry tetrahydrofuran solution into the reaction bottle. After the addition is complete, allow the reaction to warm to room temperature naturally and stir at room temperature overnight. Add saturated ammonium chloride solution to quench the reaction, extract with dichloromethane, dry, concentrate, and use V PE :V EA =20:1 column chromatography separation to obtain 5.1 g of light yellow solid 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9,9-dimethyl-9,10-dihydroacridine M-PDD with a yield of 52%. 1 H NMR (400 MHz, CDCl 3)δ8.46(d,J=1.4Hz,1H),7.64(ddd,J=8.8,2.3,1.2Hz,1H),7.51(t,J=2.3Hz,1H),7.36(dd,J=8.7,7.9Hz,1H ),7.32–7.25(m,2H),7.23(d,J=1.4Hz,1H),7.15–7.04(m,4H),6.96–6.90(m,3H),3.83(s,3H),1.61(s,6H).

[0117]

[0118] Embodiment 18

[0119] Preparation of hydroxypyrimidine ligand 3-(6-(9,9-dimethylacridin-10(9H)-yl)pyrimidin-4-yl)phenol OH-PDD.

[0120] Weigh 10-(6-(3-methoxyphenyl)pyrimidin-4-yl)-9,9-dimethyl-9,10-dihydroacridine M-PDD (5 g, 12.7 mmol) in a round-bottom flask, inject hydrobromic acid (30 mL, 1084 mmol) and glacial acetic acid (100 mL, 890 mmol), and reflux at 120°C for 2 days. After the reaction is completed, cool to room temperature, add a large amount of ice water to the reaction solution, and a yellow-brown solid precipitates, which is filtered. Use V PE :V EA =3:1 column chromatography separation to obtain 4.3 g of yellow solid 3-(6-(9,9-dimethylacridin-10(9H)-yl)pyrimidin-4-yl)phenol OH-PDD with a yield of 88.5%. 1 H NMR (400 MHz, CDCl 3 )δ8.77(s,1H),8.46(d,J=1.4Hz,1H),7.48(ddd,J=8.6,2.3,1.2Hz,1H),7.32–7.21(m,5H),7 .15–7.04(m,4H),6.93(dt,J=6.5,1.4Hz,2H),6.81(ddd,J=8.2,2.2,1.1Hz,1H),1.61(s,6H).

[0121]

[0122] Embodiment 19

[0123] Preparation of pinene pyrimidine main ligand pinene phenoxy pyrimidine-10H-dimethyl acridine MPXP.

[0124] Weigh (6R,8R)-3-(3-bromophenyl)-pinene Br-DPTM (327.0 mg, 1.0 mmol), 3-(6-(9,9-dimethylacridin-10(9H)-yl)pyrimidin-4-yl)phenol OH-PDD (379.0 mg, 1.0 mmol), CuI (19.0 mg, 0.1 mmol), cesium carbonate (977.0 mg, 3.0 mmol), and 2-picolinic acid (0.3 g, 2.0 mmol) in a sealed tube, add 5 mL of DMSO (5 mL, 50 mmol) deoxygenated by nitrogen bubbling, evacuate and fill with nitrogen three times, and react at 120°C for 24 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, and separated by developing agent column chromatography to obtain 0.42 g of yellow powder pinene phenoxypyrimidine-10H-dimethylacridine MPXP with a yield of 67.2%. 1 H NMR (400MHz, DMSO) δ8.76 (s, 1H), 8.18 (s, 1H), 7.91 (d, J = 7.8Hz, 1H), 7.81 (dd, J = 20.7, 12.0Hz,4H),7.67(d,J=7.8Hz,1H),7.59(s,1H),7.53(t,J=9.4Hz,4H),7.43(s,1H),7.3 1(dt,J=14.7,7.0Hz,4H),7.22(d,J=8.1Hz,1H),7.13(d,J=9.8Hz,1H),3.00(s,2H),2.8 4(s,1H),2.68(s,1H),2.28(s,1H),1.99(s,1H),1.45(s,6H),1.39(s,3H),0.59(s,3H).

[0125]

[0126] Embodiment 20

[0127] Preparation of complex Pt-MDP.

[0128] Weigh the main ligand pinene phenoxy pyrimidine-10H-dimethyl acridine MPXP (125.2 mg, 0.2 mmol),

[0129] K 2 PtCl 4 (92.0mg, 0.22mmol) was placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10 minutes, and acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12 hours, and then heated to 120℃ for 72 hours. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and a red solid precipitated, which was filtered. PE :V DCM=2:1 developing solvent for column chromatography separation to obtain red powder Pt-MDP 20 mg, the yield is 12.3%. 1 H NMR (400 MHz, CDCl 3 )δ9.05(d,J=0.8Hz,1H),7.50–7.42(m,3H),7.40–7.33(m,2H),7.32–7. 25(m,2H),7.15–7.04(m,4H),6.94–6.85(m,3H),6.73(ddd,J=18.5,7.7, 1.3Hz,2H),6.61(dd,J=7.7,1.4Hz,1H),3.11–2.90(m,3H),2.01–1.87(m ,2H),1.78(dt,J=12.1,7.8Hz,1H),1.61(s,6H),0.97(d,J=16.5Hz,6H).

[0130]

[0131] Embodiment 21

[0132] Preparation of complex Pd-MDP.

[0133] Weigh the main ligand pinene phenoxy pyrimidine-10H-dimethyl acridine MPXP (125.2 mg, 0.2 mmol), Pd(OAc) 2 (42.0mg, 0.22mmol), TBAB (8.0mg, 0.1mmol) were placed in a sealed tube, vacuumed, and filled with nitrogen. Acetic acid was blown with nitrogen for 10min, acetic acid (10mL, 60mmol) was drawn and added to the sealed tube under nitrogen protection, stirred at room temperature for 12h, and then heated to 120℃ for 72h. After the reaction was completed, the reaction solution was poured into a large amount of ice water, and an orange-red solid precipitated, which was filtered. V PE :V DCM =2:1 developing solvent for column chromatography separation to obtain orange-red powder Pd-MDP40.0 mg, with a yield of 32%. 1 H NMR (400 MHz, CDCl 3)δ8.87(d,J=0.8Hz,1H),7.82(dd,J=8.2,1.4Hz,1H),7.56–7.50(m,2H),7.44 (d,J=19.4Hz,2H),7.32–7.25(m,5H),7.15–7.04(m,4H),6.91(ddd,J=7.9,6. 4,1.3Hz,2H),6.67(ddd,J=20.5,7.9,1.2Hz,2H),3.11–2.91(m,3H),2.01–1. 87(m,2H),1.78(dt,J=12.1,7.8Hz,1H),1.61(s,6H),0.97(d,J=16.5Hz,6H).

[0134]

[0135] Embodiment 22

[0136] The photophysical properties of platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP were tested in dichloromethane solution.

[0137] The UV-visible absorption and emission spectra of phosphorescent platinum (II) complex Pt-MDP and palladium (II) complex Pd-MD and Pd-MDP are shown in the attached figure. Figure 1-Figure 4 The complexes Pt-MDP, Pd-MD and Pd-MDP were prepared into 1×10 -4 mol / L dichloromethane (DCM) solution, transfer 2.5mL of complex Pt-MDP, Pd-MD and Pd-MDP solution into a fluorescence cuvette, and test their UV-visible absorption and emission spectra. The experimental results show that the three complexes have strong absorption at 230nm-400nm, mainly because 1 π-π* transition, while the complex has weak absorption at 400nm-450nm, which is mainly due to the charge transfer from singlet metal to ligand ( 1 MLCT) and spin-forbidden triplet metal-to-ligand charge transfer ( 3 MLCT). When 380nm light is used as the excitation wavelength, Figure 2 It can be seen that the maximum emission peak of the platinum (II) complex Pt-MDP is at 590nm. Figure 3 and Figure 4The results show that the palladium (II) complexes Pd-MD and Pd-MDP have the characteristics of aggregation-induced emission, and their emission spectra in water / THF mixed solutions with different volume ratios are tested. They are both insoluble in water, so when the volume ratio of water in the mixed solution gradually increases, the squeezing of water molecules causes them to aggregate, which enhances the emission. When the water / THF ratio in the solution reaches 90%, the color of the solution becomes significantly darker; and under the irradiation of a 365nm ultraviolet lamp, when the solution is completely a good solvent, it emits almost no light or only very weak light. When the water ratio is 90%, strong luminescence can be observed. Since the distance between the ligand and the complex is far in the dilute THF state, the spatial torsion of the bond is relatively free, so it has no emission in the dilute good solvent. In the aggregated state, the interaction force between molecules is enhanced, the torsion of the bond is restricted, and thus there is a strong emission in the aggregated state. The maximum emission peaks of the complexes Pd-MD and Pd-MDP in the aggregated luminescent state are both around 570nm, and they also have excellent stability. Among them, the complex Pd-MDP showed a more obvious pressure-induced color change effect. When the complex was ground, the luminescence had a red shift phenomenon. Figure 5 shown.

[0138] Embodiment 23

[0139] Density functional theory calculations of platinum(II) complex Pt-MDP and palladium(II) complexes Pd-MD and Pd-MDP.

[0140] Density functional theory (DFT) calculations were performed on the complexes Pt-MDP, Pd-MD and Pd-MDP using Gauss 06 to study the photophysical properties of these luminescent materials. Using the B3LYP method, for these three complexes, the HOMO distribution is mainly located on the central atom palladium (II) and phenyl-oxy-phenyl, while the LUMO is mainly confined to the electron acceptor pyrimidine unit. Figure 6 The atomic orbital occupancy ratio distribution diagrams of the three materials are listed. The HOMO energy levels of Pt-MDP, Pd-MD and Pd-MDP are -4.77eV, -4.97eV and -4.94eV, and the LUMO energy levels are -1.56eV, -1.54eV and -1.49eV, respectively. The theoretical energy level differences of the three complexes are 3.21eV, 3.43eV and 3.45eV, respectively.

[0141] Embodiment 24

[0142] The electrochemical properties of platinum (II) complex Pt-MDP and palladium (II) complexes Pd-MD and Pd-MDP were tested.

[0143] To investigate the HOMO and LUMO energy states and charge carrier injection properties of Pt(II) and Pd(II) complexes, we used cyclic voltammetry (CV) in dichloromethane solution with Ag / AgNO 3 The oxidation potential of the system was determined using the reference electrode. Figure 7 As shown, it can be seen that all complexes have oxidation peaks in the range of 1-1.5 V. And according to the oxidation potential and reduction potential of each complex, the corresponding HOMO energy level and LUMO energy level can be calculated, and then the energy gap E of platinum (II) complex Pt-MDP and palladium (II) complex Pd-MD and Pd-MDP can be obtained. g (The difference between the HOMO energy level and the LUMO energy level) are 2.3 eV, 2.21 eV and 2.67 eV respectively.

[0144] Embodiment 25

[0145] Fabrication of organic electroluminescent devices.

[0146] The device of the present invention using palladium (II) complexes Pd-MD and Pd-MDP as the light-emitting layer may include: the device structure is as follows Figure 8 As shown, HAT-CN (10nm) / TAPC (30nm) / TCTA (10nm) / MCP: x% Pd (25nm) / TmPyPb (35nm) / Liq (1nm) / Al, where HAT-CN is used as the hole injection layer of the device; TAPC and TCTA are used as hole transport layers, and they also have the function of adjusting energy level matching; MCP: x% Pd is the light-emitting layer, with MCP as the main material and doped with different concentrations of palladium (II) complexes; TmPyPb is used as the electron transport layer; Liq also plays a role in adjusting the energy level, and finally Al is used as the cathode of the device. The organic electroluminescent device with Pd-MD as the light-emitting layer, among which the device doped with 15wt% has the best performance, with a maximum current efficiency of 34.52cd / A, a power efficiency of 19.72lm / W, and an external quantum efficiency of 9.37%. In particular, its non-doped device still maintains a good efficiency of 9.61cd / A, 5.45lm / W and 9.88%. The electroluminescent spectrum, current density-voltage-brightness, brightness-current efficiency and brightness-external quantum efficiency curves of its electroluminescent device are shown in the attached figure. Fig. 9 Attached Fig.10The electroluminescence spectra, current density-voltage-brightness, brightness-current efficiency and brightness-external quantum efficiency curves of Pd-MDP at 5%, 10%, 15%, 20% and 100% doping concentrations are shown in the figure. The device has the best performance, with a maximum current efficiency of 42.44cd / A, a power efficiency of 24.24lm / W and an external quantum efficiency of 14.18%. Its non-doped device still maintains a good efficiency of 12.53cd / A, 7.88lm / W and 7.03%. The above data show that constructing this complex containing a large steric hindrance of pinene structure and DA structure can obtain a high-efficiency device.

[0147] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A pinene pyrimidine tetradentate platinum (II) and palladium (II) complex, characterized in that: The complex is an asymmetric chiral tetradentate complex based on the pyrimidine ligand of pinene. The general structural formula of the complex is a compound represented by the following formula (I) and formula (II): Among them, R is one of N-carbazolyl, N-diphenylamino, N-phenothiazinyl, N-phenoxazinyl, N-dimethylacridinyl, 2,6-dimethyl substituted phenoxy, 2,6-diisopropyl substituted phenoxy, and hexahydropyridinyl.

2. A method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 1, characterized in that: The following steps are involved: Under nitrogen protection, potassium tetrachloroplatinate and pinene pyrimidine ligands are dissolved in acetic acid, a catalyst is added, the reaction is carried out at room temperature in the dark, and then the temperature is raised to react to obtain a pinene pyrimidine tetradentate platinum (II) complex as shown in formula (I); Under nitrogen protection, palladium acetate and pinene pyrimidine ligands are dissolved in acetic acid, a catalyst is added, and the reaction is carried out at room temperature in the dark, and then the temperature is raised to react to obtain a pinene pyrimidine tetradentate palladium (II) complex as shown in formula (II).

3. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, characterized in that: The molar ratio of raw materials used for preparing pinene pyrimidine tetradentate platinum (II) complex is: potassium tetrachloroplatinate: catalyst: pinene pyrimidine ligand: acetic acid = 1.0-1.5: 1-5: 1: 100-500.

4. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, characterized in that: The molar ratio of raw materials used for preparing pinene pyrimidine tetradentate palladium (II) complex is: palladium acetate: catalyst: pinene pyrimidine ligand: acetic acid = 1.0-1.5: 1-5: 1: 100-500.

5. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, characterized in that: The catalyst is one of potassium acetate, sodium acetate and ammonium acetate.

6. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 2, characterized in that: The specific steps include: The pyrimidine compound shown in formula (1) and the pinene compound shown in formula (2) are dissolved in an organic solvent, and reacted at 100-130° C. for 20-40 hours in the presence of cuprous iodide and a base to obtain a pinene pyrimidine chiral asymmetric tetradentate ligand shown in formula (3); Under nitrogen protection, a pinene pyrimidine chiral asymmetric tetradentate ligand as shown in formula (3) and potassium tetrachloroplatinate are dissolved in acetic acid, a catalyst is added, and the mixture is stirred at room temperature in the dark for 6 to 12 hours, and then the temperature is raised to 120 to 150° C. for reaction for 18 to 72 hours to obtain a pinene pyrimidine tetradentate palladium (II) complex as shown in formula (I); Under nitrogen protection, the pinene pyrimidine chiral asymmetric tetradentate ligand and palladium acetate as shown in formula (3) are dissolved in glacial acetic acid, a catalyst is added, and the mixture is stirred at room temperature in the dark for 6 to 12 hours, and then the temperature is raised to 120 to 150° C. and reacted for 18 to 72 hours to obtain the pinene pyrimidine tetradentate palladium (II) complex as shown in formula (II).

7. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, characterized in that: The molar ratio of the raw materials used to prepare the pinene pyrimidine chiral asymmetric tetradentate ligand shown in formula (3) is: pyrimidine compound shown in formula (1): pinene compound shown in formula (2): organic solvent: cuprous iodide: base = 1:1:10-50:0.01-0.1:1-10.

8. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, characterized in that: The organic solvent used to prepare the pinene pyrimidine chiral asymmetric tetradentate ligand as shown in formula (3) is one of toluene, dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran and 1,4-dioxane.

9. The method for preparing the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 6, characterized in that: The base used to prepare the pinene pyrimidine chiral asymmetric tetradentate ligand shown in formula (3) is one of potassium carbonate, sodium carbonate, sodium tert-butoxide, potassium tert-butoxide, potassium phosphate and cesium carbonate.

10. Use of the pinene pyrimidine tetradentate platinum (II) and palladium (II) complex according to claim 1, characterized in that: It is used as a light-emitting layer in electroluminescent devices, or in the fields of sensors, anti-counterfeiting, storage and display.

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