Circularly polarized phosphorescent Pt (II) complex as well as preparation method and application thereof

Abstract

The invention relates to the technical field of luminescent materials, in particular to a circularly polarized phosphorescent Pt (II) complex as well as a preparation method and application thereof. The circularly polarized phosphorescent Pt (II) complex has a structure as shown in a formula (R)-I, a formula (S)-I, a formula (R)-II, a formula (S)-II, a formula (R)-III or a formula (S)-III, according to the invention, [2.2] paracyclophane is mainly used as a planar chiral skeleton, and different sites of the planar chiral skeleton are modified to obtain the circularly polarized phosphorescent Pt (II) complex which is stable in chirality and is not easy to racemize. The high-efficiency circularly polarized phosphorescent Pt (II) complex with both luminous quantum yield and circular polarization property is obtained by utilizing the advantages of a four-coordinate plane structure, high exciton utilization rate and adjustable color of the Pt (II) complex, and the high-efficiency circularly polarized phosphorescent Pt (II) complex has great research value on development of circularly polarized chiral materials. .

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to a circularly polarized phosphorescent Pt(II) complex and a preparation method and application thereof. Background Art

[0002] Circularly polarized luminescence (CPL) is an emerging next-generation optoelectronics technology, showing promising applications in 3D displays, optical information storage, and asymmetric synthesis. Circularly polarized electroluminescent materials play a key role in circularly polarized organic light-emitting diodes (COLEDs). Circularly polarized organic light-emitting diodes (CP-OLEDs) are also known as circularly polarized organic light-emitting diodes (COLEDs).

[0003] In recent years, research on CPL materials has made significant progress, with numerous CPL materials demonstrating high luminescence performance, high asymmetry factors, and high quantum efficiency reported. However, current research on CPL materials has primarily focused on fluorescent CPL materials, with limited research on circularly polarized phosphorescent materials. This situation, primarily due to the instability of triplet excitons, presents significant challenges in combining CPL with phosphorescent materials. However, CPL phosphorescent materials, combining the characteristics of both CPL and phosphorescent materials, have shown significant application potential in advanced information security materials and bioimaging.

[0004] [2.2] Paracyclophane, the English name is [2,2] Paracyclophane, referred to as PCP, the chemical name is p-xylene dimer, the molecular formula is C 16 H 16 . PCP is a typical planar chiral skeleton with two coplanar stacked and strongly interacting benzene units, which provides a conformationally rigid chiral environment due to the restriction of the free rotation of the phenylene groups. Due to the above characteristics, PCP has a wide range of applications in asymmetric catalysis, supramolecular macrocyclic compounds and chiral luminescent materials. Within the PCP skeleton, the electronic coupling between the donor and acceptor groups can be regulated by the π-π stacking interaction of the two aromatic hydrocarbons, and the π-π stacking enhances the delocalization of the highest occupied molecular orbital, thereby increasing the donor strength. More notably, PCP provides a stereo scaffold for derivatives substituted at its specific positions and exhibits unique chiral optical properties in circular dichroism and CPL spectra. These properties make it have great development potential in future optical material applications related to circularly polarized light and spin electronics.

[0005] However, the application of this planar chiral unit in CPL materials still needs to be improved in many aspects. Recently, researchers reported that by connecting a phenothiazine donor and a 2,4,6-triphenyl-1,3,5-triazine acceptor to the 4- and 7-positions of the PCP unit, respectively, the prepared device achieved yellow emission with a maximum external quantum efficiency of 20.1% and an electroluminescence asymmetry factor of 1.5×10 −3 / -1.3×10 −3 However, the structure-activity relationship between the molecular structure and the luminescence asymmetry factor reported in current studies is unclear, and the reported double-helical macrocycle based on planar chiral [2.2]-cyclophane has a relatively low quantum yield of only 51%. Therefore, in order to fully demonstrate the research progress of PCP derivatives, it is of great significance to develop more efficient CPL materials based on PCP units. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a circularly polarized phosphorescent Pt(II) complex based on [2.2] paracyclophane, as well as a preparation method and application. The present invention establishes a relatively complete structure-activity law of the influence of the material molecular skeleton, functional group structure and substitution position on the asymmetric factor, and the high asymmetric factor of the circularly polarized phosphorescent Pt(II) complex of the present invention reaches g lum =1.2 10 -3 , and the quantum yield reaches Φ em =83.71%, which has the beneficial effects of high quantum yield and high asymmetry factor, and is of great research value for the development of circularly polarized chiral materials.

[0007] To achieve the above objectives, the technical solutions of the present invention are as follows.

[0008] In a first aspect, the present invention provides a circularly polarized phosphorescent Pt(II) complex having a structure represented by the following formula (R)-I, formula (S)-I, formula (R)-II, formula (S)-II, formula (R)-III or formula (S)-III: ; Wherein, formula (R)-I and formula (S)-I are a pair of chiral enantiomers; formula (R)-II and formula (S)-II are a pair of chiral enantiomers; formula (R)-III and formula (S)-III are a pair of chiral enantiomers; the Ar group is an azaaryl group or a benzazaaryl group; -D(A) represents a group D or a group A; the group D represents an electron-rich donor group, and the group A represents an electron-deficient acceptor group; the group D is any one of a diphenylamine group and a carbazole group; and the group A is any one of a di(mesityl)boryl group and a 4,6-diphenyl-1,3,5-triazine-2-yl group.

[0009] Preferably, the Ar group is any one of pyridyl, pyrazinyl, pyrimidinyl, quinolyl and isoquinolyl.

[0010] Preferably, the circularly polarized phosphorescent Pt(II) complex is selected from any one of the following compounds: .

[0011] The second aspect of the present invention provides a method for preparing the circularly polarized phosphorescent Pt(II) complex described in the first aspect, comprising the following steps: Under an inert gas atmosphere, the halogen-substituted [2.2]-cyclophane reacts with the 4-tri-n-butyltin-based Ar ring in the presence of lithium chloride, cuprous chloride and a first palladium catalyst to undergo a C-C bond coupling reaction to obtain the Ar ring-substituted [2.2]-cyclophane.

[0012] Under an inert gas atmosphere, the Ar ring-substituted [2.2]-cyclophane reacts with AX in the presence of n-butyl lithium to undergo CC coupling reaction or CB coupling reaction to obtain the Ar ring- and group A-substituted [2.2]-cyclophane; the Ar ring- and group A-substituted [2.2]-cyclophane reacts with potassium chloroplatinite and sodium acetylacetonate to obtain a racemic circularly polarized phosphorescent Pt(II) complex.

[0013] Alternatively, under an inert gas atmosphere, the Ar ring-substituted [2.2]-cyclophane is reacted with DH in the presence of a second palladium catalyst, a phosphine ligand, and a base to undergo a CN coupling reaction to obtain the Ar ring- and group-D-substituted [2.2]-cyclophane; the Ar ring- and group-D-substituted [2.2]-cyclophane is reacted in the presence of potassium chloroplatinite and sodium acetylacetonate to obtain a racemic circularly polarized phosphorescent Pt(II) complex.

[0014] The racemic circularly polarized phosphorescent Pt (II) complex is separated by a high performance liquid chiral chromatography column to be split into chiral enantiomers to obtain a chiral circularly polarized phosphorescent Pt (II) complex.

[0015] The specific reaction equation is as follows: ; Among them, the halogen-substituted [2.2]-cyclophane is a compound represented by formula IV-1, formula IV-2 or formula IV-3; the 4-tri-n-butyltin-based Ar ring is Ar-SnBu3; X is a halogen; R1 and R2 are independently selected from halogens; the Ar ring-substituted [2.2]-cyclophane is a compound represented by formula V-1, formula V-2 or formula V-3; the Ar ring and group D(A)-substituted [2.2]-cyclophane is a compound represented by formula VI-1, formula VI-2 or formula VI-3; the racemic circularly polarized phosphorescent Pt(II) complex is a compound represented by formula (R / S)-I, formula (R / S)-II or formula (R / S)-III.

[0016] Preferably, R1 and R2 are independently selected from I, F or Br; and X is F.

[0017] Preferably, the first palladium catalyst is tetrakistriphenylphosphine palladium; the second palladium catalyst is any one of palladium acetate, tetrakistriphenylphosphine palladium and tris(dibenzylideneacetone)dipalladium; the phosphine ligand is any one of tri-tert-butylphosphine, X-Phos, Ru-Phos and S-Phos; and the base is any one of potassium carbonate, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide.

[0018] Preferably, the molar ratio of the halogen-substituted [2.2]-cyclophane, 4-tri-n-butyltin-based Ar ring, lithium chloride, cuprous chloride and the first palladium catalyst is 1:1.2~1.5:1~1.5:1~1.5:0.02~0.05; the molar ratio of the Ar ring-substituted [2.2]-cyclophane, AX and n-butyllithium is 1:1~1.5:1~1.2; the molar ratio of the Ar ring-substituted [2.2]-cyclophane, DH, the second palladium catalyst, the phosphine ligand and the base is 1:1.2~1.5:0.02~0.05:0.06~0.15:2~3; the molar ratio of the Ar ring and the group D(A)-substituted [2.2]-cyclophane, potassium chloroplatinite and sodium acetylacetonate is 1.05~1.2:1:2.2~2.5.

[0019] Preferably, in the process of preparing the Ar ring-substituted [2.2]-cyclophane, the first solvent is N,N-dimethylformamide, the reaction temperature is 100°C, and the reaction time is 16 hours; in the process of preparing the Ar ring and group A-substituted [2.2]-cyclophane, the second solvent is tetrahydrofuran, the reaction temperature is room temperature, and the reaction time is 16 hours; in the process of preparing the Ar ring and group D-substituted [2.2]-cyclophane, the third solvent is N,N-dimethylformamide, the reaction temperature is 120°C, and the reaction time is 16 hours; in the process of preparing the racemic circularly polarized phosphorescent Pt(II) complex, the fourth solvent is a mixed solution of ethylene glycol ethyl ether and water, and the volume ratio of ethylene glycol ethyl ether to water is 2.5~3.5:1, the reaction temperature is 60°C~75°C, and the reaction time is 1.5h~2h.

[0020] Preferably, the inert gas is any one of nitrogen and argon.

[0021] The third aspect of the present application provides an application of the circularly polarized phosphorescent Pt(II) complex of the first aspect as a circularly polarized luminescent material.

[0022] The beneficial effects of the present application are: 1. The present application mainly uses [2.2]paracyclophane as a planar chiral skeleton, and obtains a circularly polarized phosphorescent Pt(II) complex with stable chirality and difficult to racemize by modifying different sites of the planar chiral skeleton.

[0023] 2. The present application uses the advantages of the four-coordinated planar structure of the Pt(II) complex, high exciton utilization rate and color adjustability to obtain a high-efficiency circularly polarized phosphorescent Pt(II) complex with both high luminescent quantum yield and circular polarization characteristics, and the high asymmetric factor of the circularly polarized phosphorescent Pt(II) complex of the present application reaches g lum =1.2 10 -3 , and the quantum yield reaches Φ em =83.71%, which has the beneficial effects of high quantum yield and high asymmetric factor, and has great research value for the development of circularly polarized chiral materials.

[0024] 3. The present application provides a method for preparing chiral disubstituted [2.2]paracyclophane complexes of different sites based on the low reactivity of [2.2]paracyclophane, which has limited modification methods. The raw materials are cheap and easy to obtain, the synthesis method is simple and easy to operate, and the product yield is high and easy to separate. The circularly polarized phosphorescent Pt(II) complex provided by the present application has the characteristics of easy derivatization, and the chirality is stable and difficult to racemize, which has good application prospect in the field of chiral optoelectronic materials. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is a synthesis route diagram of the target Pt(II) complex prepared by the present application.

[0026] Figure 2 is a circular dichroism spectrum of the target Pt(II) complex provided by the present application. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below combined with examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0028] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0029] The circularly polarized phosphorescent Pt(II) complexes of the present invention are mainly chiral 4,7-disubstituted [2.2]-p-cyclophane, 4,16-disubstituted [2.2]-p-cyclophane complexes and 4,12-disubstituted [2.2]-p-cyclophane complexes, and the specific general structural formulas are as follows: .

[0030] Among them, group A is an electron-deficient acceptor group, which can be selected from any one of di(mesityl)boron fluoride and 2-chloro-4,6-diphenyl-1,3,5-triazine; group D is an electron-rich donor group, which comes from any one of diphenylamine and carbazole; and the Ar ring can be selected from a six-membered nitrogen heterocycle such as pyridine, pyrazine, pyrimidine, quinoline or isoquinoline.

[0031] The complexes of 4,7-disubstituted [2.2]-p-cyclophane and 4,16-disubstituted [2.2]-p-cyclophane are a pair of racemates, which can be separated into R and S configurations by chiral liquid chromatography column.

[0032] The present invention provides a class of circularly polarized phosphorescent Pt(II) complexes based on [2.2] paracyclophane (PCP). The PCP group provides a chiral center, and the molecules modified at the 4, 7 / 4, 12 / 4, and 16 positions have a chiral structure. The multi-site chirality characteristics of the PCP group are utilized to explore the effects of modification at different chiral sites on its quantum yield and chiral signal, which has reference value for the subsequent application of PCP in the field of chiral luminescent materials.

[0033] The preparation method of a circularly polarized phosphorescent Pt(II) complex comprises the following steps: Step 1: Synthesis of an intermediate based on 4,7-disubstituted [2.2]-cyclophane, specifically: Step 1.1: Dissolve [2.2]-paracyclophane in dichloromethane and stir at 0-5°C for 1 hour. Then, add concentrated nitric acid and concentrated sulfuric acid dropwise at the same temperature and continue the reaction for 2 hours. After the reaction, pour into water and extract three times with dichloromethane. Dry the organic phase over anhydrous sodium sulfate and concentrate in vacuo to obtain a crude product, which is then separated by column chromatography to yield compound A1.

[0034] In Step 1.2, the compound represented by Formula A1 is dissolved in ethanol with stannous chloride and concentrated hydrochloric acid. The reaction mixture is reacted at 90°C for 4 hours. After the reaction, the mixture is cooled to room temperature and poured into aqueous NaOH solution. The mixture is then extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to yield Compound A2.

[0035] In step 1.3, the compound represented by formula A2 and di-tert-butyl dicarbonate are dissolved in ethanol, and the reaction mixture is reacted at 50-60°C for 5 hours. After the reaction, the mixture is precipitated with petroleum ether and centrifuged to obtain the compound represented by formula A3.

[0036] In Step 1.4, the compound represented by Formula A3, pyridine hydrobromide, and iodobenzene diacetate are dissolved in acetonitrile. The reaction mixture is reacted at 50-60°C overnight. After completion of the reaction, the mixture is poured into water and extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is then separated by column chromatography to afford Compound A4.

[0037] Step 1.5: React the compound represented by Formula A4 with trifluoroacetic acid in dichloromethane at room temperature for 2 h. After completion of the reaction, pour the mixture into water and extract three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain the compound represented by A5.

[0038] In Step 1.6, the compound of Formula A5 and fluoroboric acid are stirred in ethanol until the solution is clear. Isoamyl nitrite is added at -5-0°C and allowed to react for 2 hours. After filtration, the solid is poured into a solution of potassium iodide in acetonitrile and allowed to react for 2 hours. After completion of the reaction, the mixture is poured into water and extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to yield a crude product, which is then separated by column chromatography to afford Compound A6.

[0039] .

[0040] Step 2: Synthesis of an intermediate based on 4,16-disubstituted [2.2]-cyclophane, specifically: Dissolve [2.2]-paracyclophane in carbon tetrachloride and heat to 55°C. Then, add liquid bromine dropwise and react for 2 hours. After the reaction, add aqueous sodium sulfite solution and extract three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product. Recrystallize from 1,4-dioxane to obtain the compound represented by Formula B1.

[0041] Step 3: Synthesize organic ligands based on 4,7-disubstituted [2.2]-cyclophane, 4,12-disubstituted [2.2]-cyclophane and 4,16-disubstituted [2.2]-cyclophane, specifically: Step 3.1. Under an inert gas atmosphere, the compound represented by Formula A6 / B1 / B2 is dissolved with lithium chloride, cuprous chloride, tetrakis(triphenylphosphine)palladium, and 4-tri-n-butyltin-based six-membered nitrogen heterocycle in an ultra-dry N,N-dimethylformamide solvent. The reaction is carried out at 100°C for 16 hours. After the reaction, the temperature is cooled to room temperature and poured into water. The mixture is extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is then separated by column chromatography to obtain the compounds represented by Formulas C1, C2, and C3.

[0042] Formula B1 Formula B2 .

[0043] The 4-tri-n-butyltin-based six-membered nitrogen heterocycle is one of pyridine, pyrazine, pyrimidine, quinoline or isoquinoline.

[0044] Step 3.2. Under an inert gas atmosphere, the compound represented by Formula C1 / C2 / C3 is dissolved in tetrahydrofuran solvent and reacted with n-butyl lithium at -78°C for 1 h. AX is then added and the reaction is carried out at room temperature overnight. After the reaction is completed, the mixture is poured into water and extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is then separated by column chromatography to obtain compounds represented by Formulas C4, C5, and C6.

[0045] .

[0046] In formula AX, group A is an electron-deficient acceptor group selected from any one of di(mesityl)boron fluoride and 2-chloro-4,6-diphenyl-1,3,5-triazine.

[0047] In step 3.3, the compounds represented by formula C1 / C2 / C3 undergo CN coupling reaction or CC coupling reaction with an electron-rich donor to obtain compounds represented by formula C7, C8, or C9.

[0048] .

[0049] The group D in formula C7 / C8 / C9 represents a group derived from the electron-rich donor; the electron-rich donor is any one of diphenylamine and carbazole.

[0050] Step 4: Synthesize chiral phosphorescent Pt(II) complexes based on 4,7-disubstituted [2.2]-cyclophane, 4,12-disubstituted [2.2]-cyclophane and 4,16-disubstituted [2.2]-cyclophane, specifically: Under an inert gas atmosphere, the organic ligands represented by formulas C4 / C5 / C6 / C7 / C8 / C9 and potassium chloroplatinite are dissolved in a mixture of ethylene glycol ether and water. The mixture is heated to 60-75°C and reacted for 1.5-2 hours. After the reaction system cools to room temperature, it is poured into water and centrifuged, followed by drying in a vacuum oven to obtain an intermediate. The dried intermediate and sodium acetylacetonate are dissolved in dichloromethane and stirred overnight at room temperature. The crude product is separated and purified by column chromatography to obtain the target chiral phosphorescent Pt(II) complexes D1, D2, D3, D4, D5, and D6.

[0051] .

[0052] The technical solution of the present invention is further described below through specific embodiments.

[0053] In the following examples, the methods described are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0054] Example 1 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0055] Refer to the attached Figure 1 , a method for preparing a circularly polarized phosphorescent Pt(II) complex, comprising the following steps: Step 1, Preparation of the Compound of Formula A1: Dissolve 1.0 equiv. of [2.2]-paracyclophane in dichloromethane and stir at 0°C to 5°C for 1 hour. Then, add 4.0 equiv. of concentrated nitric acid and 2.0 equiv. of concentrated sulfuric acid dropwise at the same temperature and continue the reaction for 2 hours. After the reaction, pour the mixture into water and extract three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The crude product is separated and purified by column chromatography using a 1:1 volume ratio of n-hexane to dichloromethane as the eluent to obtain the compound of Formula A1 in a 70% yield. 1 H NMR (400 MHz, CHCl3- d ) δ 7.19(s, 1H), 6.76 (d, 1H), 6.56 (m, 4H), 6.44 (d, 1H), 3.99 (m, 1H), 3.16 (m,4H), 3.14 (m, 2H), 2.87 (m, 1H).

[0056] Step 2, Preparation of the Compound of Formula A2: Dissolve 1.0 equiv of the compound of Formula A1 with 3.5 equiv of stannous chloride and 3.0 equiv of concentrated hydrochloric acid in ethanol. The reaction mixture is reacted at 90°C for 4 hours. After the reaction is completed, the mixture is cooled to room temperature and poured into aqueous sodium hydroxide solution. The mixture is then extracted three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain the compound of Formula A2 in a 90% yield. 1 H NMR (400 MHz, CHCl3- d) δ 7.17 (d, 1H), 6.59 (d,1H), 6.39 (d, 2H), 6.27 (d, 1H), 6.13 (d, 1H), 5.40 (s, 1H), 3.50 (br, 1H), 3.01 (m, 6H), 2.84 (m, 1H), 2.66 (m, 1H).

[0057] Step 3, Preparation of the Compound of Formula A3: Dissolve 1.0 equiv. of the compound of Formula A2 and 1.5 equiv. of di-tert-butyl dicarbonate in ethanol. React the reaction mixture at 50°C-60°C for 5 h. After the reaction, precipitate with petroleum ether and centrifuge to obtain the compound of Formula A3 in a 90% yield. 1 H NMR (400 MHz, CHCl3- d ) δ 6.80 (d,1H), 6.73 (s, 1H), 6.52 (m, 2H), 6.43 (d, 1H), 6.37 (d, 1H), 6.25 (s, H,),3.24 (d, 1H,), 3.15 (m, 1H,), 3.04(m, 5H), 2.77 (d, 1H), 1.57 (s, 9H).

[0058] Step 4, Preparation of the Compound of Formula A4: Dissolve 1.0 equiv of the compound of Formula A3 with 1.5 equiv of pyridine hydrobromide and 1.5 equiv of iodobenzene diacetate in acetonitrile. The reaction mixture is reacted at 50°C-60°C overnight, i.e., for 16 hours. After the reaction, pour the mixture into water and extract three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is then separated by column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 3:1 as the eluent to obtain the compound of Formula A4 in a 49% yield. 1 H NMR (400 MHz, CHCl3- d ) δ 7.11 (d, 1H), 6.78 (s, 1H), 6.77 (s, 1H), 6.50 (d, 1H), 6.44 (s, 1H), 6.41 (d, 1H), 6.30 (s, 1H), 3.36(d, 1H), 3.14 (d, 3H), 3.00 (d, 2H), 2.73 (d, 1H), 2.61 (d, 1H), 1.54 (s,9H).

[0059] Step 5, Preparation of the Compound of Formula A5: 1.0 equiv of the compound of Formula A4 was reacted with 1.5 equiv of trifluoroacetic acid in dichloromethane at room temperature for 2 hours. After completion of the reaction, the mixture was poured into water and extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to obtain the compound of Formula A5 in a 90% yield. 1 H NMR (400 MHz, CHCl3- d )δ 7.14 (t, 2H), 6.41 (d, 2H), 6.30 (s, 1H), 5.40 (s, 1H), 3.39 (d, 2H), 3.31(d, 1H,), 3.18 (m, 1H,), 3.08 (m, 2H,), 3.00(t, 2H), 2.50 (m, 2H).

[0060] Step 6, Preparation of the Compound of Formula A6: 1.0 equiv. of the compound of Formula A5 and 3.0 equiv. of fluoroboric acid were stirred in ethanol until the solution was clear. 3.0 equiv. of isoamyl nitrite was added at -5°C to 0°C and allowed to react for 2 hours. After filtration, the solid was poured into a solution of 2.0 equiv. of potassium iodide in acetonitrile and allowed to react for 2 hours. After the reaction, the solution was poured into water and extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which was then separated by column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 100:1 as the eluent to obtain the compound of Formula A6 in a 70% yield. 1 H NMR (400MHz, CHCl3- d ) δ 7.23 (s, 1H), 7.18 (d, 1H), 6.77 (s, 1H), 6.47 (d, 2H), 6.43(s, 1H), 3.31 (m, 2H,), 3.21 (m, 2H,), 3.07 (d, 2H,), 2.82(m,1H), 2.69(d,1H).

[0061] Step 7, Preparation of compound shown as Formula CI: Compound shown as Formula A6 1.0 equiv. was dissolved in super dry N,N-dimethylformamide solvent with lithium chloride 1.0 equiv., cuprous chloride 1.0 equiv., tetrakis triphenylphosphine palladium 0.05 equiv. and 4-tri-n-butylstannylpyridine 1.2 equiv. under inert gas atmosphere, reacted at 100 °C for 16 h, after the reaction was completed, it was cooled to room temperature and poured into water, extracted with dichloromethane for three times, the organic phase was dried over anhydrous sodium sulfate, concentrated under vacuum to obtain the crude product which was separated by column chromatography, the eluent was n-hexane and ethyl acetate mixed according to the volume ratio of 100:3, to obtain the compound shown as Formula CI, the yield was 30%. 1 H NMR (400 MHz, CHCl3- d ) δ 8.69 (d, 1H), 7.71 (t, 1H), 7.44 (t, 1H), 7.18 (d, 2H), 6.75 (m, 1H), 6.55 (m, 4H), 3.63 (m, 1H), 3.41 (m, 1H), 3.13 (m, 2H), 2.89 (t, 1H), 2.76 (m, 2H), 2.54 (d, 1H).

[0062] Step 8, Preparation of compound shown as Formula a0: Compound shown as Formula CI 1.0 equiv. was dissolved in super dry N,N-dimethylformamide solvent with diphenylamine 1.2 equiv., tris(dibenzylideneacetone)dipalladium 0.05 equiv., tri-tert-butylphosphine tetrafluoroborate 0.15 equiv. and potassium tert-butoxide 2.0 equiv. under inert gas atmosphere, reacted at 120 °C for 16 h, after the reaction was completed, it was cooled to room temperature and poured into water, extracted with dichloromethane for three times, the organic phase was dried over anhydrous sodium sulfate, concentrated under vacuum to obtain the crude product which was separated by column chromatography, the eluent was n-hexane and dichloromethane mixed according to the volume ratio of 2:1, to obtain the compound shown as Formula a0, the yield was 56%. 1 H NMR (400 MHz, CHCl3- d ) δ 8.71 (m, 1H), 7.73 (t, 1H), 7.51 (d, 1H), 7.18 (m, 2H), 7.12 (s, 8H), 6.70 (m, 3H), 6.42 (m, 3H), 5.74 (s, 1H), 3.71 (t, 1H), 3.06 (d, 2H), 2.81 (m, 2H), 2.56 (m, 3H).

[0063] Step 9, Preparation of a Circularly Polarized Phosphorescent Pt(II) Complex: Under an inert atmosphere, dissolve 1.1 equiv of the organic ligand represented by Formula a0 and 1.0 equiv of potassium chloroplatinite in a mixture of ethylene glycol ether and water. The mixture is heated to 60°C–75°C and reacted for 1.5–2 hours. After cooling to room temperature, the reaction mixture is poured into water and centrifuged. The mixture is then dried in a vacuum oven to obtain an intermediate. The dried intermediate is dissolved in 2.5 equiv of sodium acetylacetonate in dichloromethane and stirred overnight at room temperature. The crude product is separated and purified by column chromatography using a 4:1 volume ratio of n-hexane to dichloromethane as the eluent to obtain the target chiral phosphorescent Pt(II) complex (R / S)-a1 in a 40% yield. 1 H NMR (400MHz, CHCl3- d ) δ 8.99 (d, 1H), 7.73 (t, 1H), 7.64 (d, 1H), 7.11 (d, 9H), 6.99(m, 1H), 6.92 (d, 1H), 6.42 (m, 3H), 5.99 (d, 1H), 5.56 (d, 1H), 5.44 (s,1H), 3.71 (d, 1H), 3.58 (d, 1H), 3.19 (m, 1H), 2.99 (m, 2H), 2.78 (d, 2H),2.53 (d, 1H), 1.97 (s, 3H), 1.77 (s, 3H). This is a racemic pair, which can be resolved into two single enantiomers (R)-a1 / (S)-a1 by high-performance liquid chromatography (HPLC) using a chiral column. The mobile phase consists of n-hexane and dichloromethane in a 4:1 volume ratio.

[0064] Example 2 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0065] Refer to the attached Figure 1 , a method for preparing a circularly polarized phosphorescent Pt(II) complex, comprising the following steps: Step 1. Preparation of the compound represented by Formula B1: Dissolve 1.0 equiv. of [2.2]-paracyclophane in carbon tetrachloride, heat to 55°C, then add 5.0 equiv. of liquid bromine dropwise and react for 2 hours. After the reaction, add aqueous sodium sulfite solution and extract three times with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product. Recrystallize from 1,4-dioxane to obtain the compound represented by Formula B1 in a 35% yield. 1 H NMR (400 MHz, CHCl3- d) δ 7.14 (d, 2H), 6.51 (d,2H), 6.44 (d, 2H), 3.49 (d, 2H), 3.16 (d, 2H), 2.89 (m, 4H).

[0066] Step 2, preparation of the compound represented by Formula C2: Under an inert gas atmosphere, 1.0 equiv. of the compound represented by Formula B1, 1.0 equiv. of lithium chloride, 1.0 equiv. of cuprous chloride, 0.05 equiv. of tetrakistriphenylphosphine palladium, and 1.2 equiv. of 4-tri-n-butyltinpyridine were dissolved in ultra-dry N,N-dimethylformamide solvent, and reacted at 100°C for 16 hours. After the reaction, the mixture was cooled to room temperature and poured into water, extracted three times with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate. The crude product obtained by vacuum concentration was separated by column chromatography using a mixture of n-hexane and ethyl acetate in a volume ratio of 100:3 as the eluent to obtain the compound represented by Formula C2 in a yield of 30%. 1 H NMR (400 MHz, CHCl3- d ) δ 8.77 (d 1H), 7.76 (t, 1H), 7.47 (d, 1H), 7.23 (s, 1H), 7.18 (d, 1H), 6.87 (s, 1H), 6.58 (m, 4H), 3.3 (m, 1H), 3.50 (d, 1H), 3.25 (m, 1H), 3.00 (m, 3H), 2.77 (m, 2H).

[0067] Step 3. Preparation of the compound represented by Formula g0: Under an inert gas atmosphere, 1.0 equiv. of the compound represented by Formula C2 was dissolved in tetrahydrofuran solvent, and 1.2 equiv. of n-butyllithium was added dropwise. The reaction was carried out at -78°C for 1 hour. Subsequently, 1.2 equiv. of di(mesityl)boron fluoride was added and the reaction was carried out at room temperature overnight, i.e., for 16 hours. After the reaction, the mixture was poured into water and extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which was separated by column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 3:1 as the eluent to obtain the compound represented by Formula g0 in a yield of 52%. 1 H NMR (400 MHz, CHCl3- d)δ 8.79 (d, 1H), 7.76 (t, 1H), 7.50 (d, 1H), 7.27 (d, 1H), 7.10 (d, 1H), 6.80(m, 5H), 6.54 (m, 1H), 6.48 (m, 2H), 6.41 (d, 1H), 3.43 (m, 1H), 3.12 (m,1H), 3.00 (m, 1H), 2.88 (m, 3H), 2.74 (m, 2H), 2.30 (s, 6H), 1.98 (m, 12H).

[0068] Step 4, Preparation of a Circularly Polarized Phosphorescent Pt(II) Complex: Under an inert atmosphere, dissolve 1.1 equiv of the organic ligand represented by formula g0 and 1.0 equiv of potassium chloroplatinite in a mixture of ethylene glycol ether and water. The mixture is heated to 60°C–75°C and reacted for 1.5–2 hours. After cooling to room temperature, the reaction mixture is poured into water and centrifuged. The mixture is then dried in a vacuum oven to obtain an intermediate. The dried intermediate is dissolved in 2.5 equiv of sodium acetylacetonate in dichloromethane and stirred overnight at room temperature. The crude product is separated and purified by column chromatography using a 5:1 volume ratio of n-hexane to dichloromethane as the eluent to obtain the target chiral phosphorescent Pt(II) complex (R / S)-g1 in a 40% yield. 1 H NMR (400MHz, CHCl3- d ) δ 9.12 (d, 1H), 7.77 (m, 2H), 7.04 (d, 2H), 6.88 (d, 1H), 6.80(d, 4H), 6.15 (d, 3H), 5.48 (s, 1H), 4.00 (m, 1H), 3.73 (m, 1H), 2.97 (m,2H), 2.84 (m, 3H), 2.63 (m, 1H), 2.28 (d, 6H), 2.00 (s, 3H), 1.90 (s, 3H),1.56 (s, 12H). This is a racemic pair, which can be separated into two single enantiomers (R)-g1 / (S)-g1 by high-performance liquid chromatography. The volume ratio of n-hexane to ethyl acetate in the mobile phase was 10:1.

[0069] Example 3 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0070] Refer to the attached Figure 1, a method for preparing a circularly polarized phosphorescent Pt(II) complex, comprising the following steps: Step 1. Preparation of the compound represented by Formula C3: Under an inert gas atmosphere, 1.0 equiv. of the commercially available compound represented by Formula B2 was dissolved with 1.0 equiv. of lithium chloride, 1.0 equiv. of cuprous chloride, 0.05 equiv. of tetrakistriphenylphosphine palladium, and 1.2 equiv. of 4-tri-n-butyltinpyridine in an ultra-dry N,N-dimethylformamide solvent. The reaction was carried out at 100° C. for 16 hours. After the reaction, the mixture was cooled to room temperature and poured into water. The mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which was separated by column chromatography using a mixture of n-hexane and ethyl acetate in a volume ratio of 100:3 as the eluent to obtain the compound represented by Formula C3 in a yield of 30%. 1 H NMR (400 MHz, CHCl3- d ) δ 8.77 (d, 1H), 7.77 (m, 1H),7.50 (m, 1H), 7.20 (m, 1H), 6.85 (d, 1H), 6.54 (m, 5H), 3.63 (m, 2H), 3.22(d, 1H), 3.11 – 2.92 (m, 3H), 2.75 (m, 2H).

[0071] Step 2, preparation of the compound represented by Formula i0: Under an inert gas atmosphere, 1.0 equiv. of the compound represented by Formula C3, 1.2 equiv. of diphenylamine, 0.05 equiv. of trisdibenzylideneacetone dipalladium, 0.15 equiv. of tri-tert-butylphosphine tetrafluoroborate, and 2.0 equiv. of potassium tert-butoxide were dissolved in ultra-dry N,N-dimethylformamide solvent, and the reaction was carried out at 120° C. for 16 h. After the reaction, the temperature was cooled to room temperature and poured into water. The mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which was separated by column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 2:1 as the eluent to obtain the compound represented by Formula i0 in a yield of 56%. 1 H NMR (400 MHz, CHCl3- d ) δ 8.54 (d, 1H), 7.43 (m, 2H), 7.20 (d,1H), 7.07 (d, 6H), 6.96 (s, 2H), 6.82 (d, 2H), 6.59 (m, 4H), 6.23 (s, 1H), 5.65 (s, 1H), 3.50 (m, 1H), 3.31 (m, 1H), 3.11 (m, 3H), 3.01 (m, 1H), 2.78(m, 2H).

[0072] Step 3, Preparation of Circularly Polarized Phosphorescent Pt(II) Complex: Dissolve the organic ligand shown in formula i0 1.1 equiv. and potassium chloroplatinate 1.0 equiv. in a mixed solution of ethylene glycol ethyl ether and water under inert gas atmosphere, and heat the mixture to 60-75 °C for 1.5-2 h. After the reaction system is cooled to room temperature, pour it into water and centrifuge, and then dry in a vacuum drying oven to obtain an intermediate. Dissolve the dried intermediate and sodium acetylacetonate 2.5 equiv. in dichloromethane solvent, and stir at room temperature overnight. Use column chromatography to separate and purify the crude product, and the eluent is a mixture of n-hexane and dichloromethane in a volume ratio of 4:1, to obtain the target chiral phosphorescent Pt(II) complex (R / S)-i1 with a yield of 40%. 1 H NMR (400 MHz, CHCl3- d ) δ 9.12 (d, 1H), 7.34 (t, 3H), 7.19 (d, 1H), 7.08 (d, 2H),6.97 (m, 3H), 6.89 (t, 1H), 6.79 (d, 2H), 6.70 (d, 1H), 6.29 (m, 4H), 5.69(s, 1H), 5.55 (s, 1H), 4.37 (m, 1H), 3.45 (m, 1H), 3.13 (m, 1H), 2.85 (m,5H), 2.06 (s, 3H), 1.98 (s, 3H). This is a pair of racemates, which can be separated into two single enantiomers (R)-i1 / (S)-i1 by high-performance liquid chiral chromatography column. The volume ratio of n-hexane and dichloromethane in the mobile phase is 4:1.

[0073] Example 4 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0074] Referring to the accompanying Figure 1 , the preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 1, the difference is that the diphenylamine of Example 1 is replaced by carbazole, and the complexes (R)-b1, (S)-b1 can be obtained.

[0075] Example 5 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0076] Referring to the accompanying Figure 1The preparation method of the circularly polarized phosphorescent Pt(II) complex is as follows: the compound represented by formula C1 is prepared according to the preparation method of Example 1. Subsequently, the preparation method of Example 2 is followed, and the compound represented by formula C2 in Example 2 is replaced by the compound represented by formula C1 to obtain complexes (R)-c1 and (S)-c1.

[0077] Example 6 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0078] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 5, except that the di(mesityl)boron fluoride in Example 5 is replaced by 2-chloro-4,6-diphenyl 1,3,5-triazine to obtain complexes (R)-d1 and (S)-d1.

[0079] Example 7 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0080] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 2, except that the di(mesityl)boron fluoride in Example 2 is replaced by 2-chloro-4,6-diphenyl 1,3,5-triazine to obtain complexes (R)-h1 and (S)-h1.

[0081] Example 8 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0082] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is as follows: the compound represented by formula C2 is prepared according to the preparation method of Example 2. Subsequently, the preparation method of Example 1 is followed, and the compound represented by formula C1 in Example 1 is replaced by the compound represented by formula C2 to obtain complexes (R)-e1 and (S)-e1.

[0083] Example 9 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0084] Refer to the attached Figure 1The preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 8. At the same time, the diphenylamine in Example 8 is replaced by carbazole to obtain complexes (R)-f1 and (S)-f1.

[0085] Example 10 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0086] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 3. At the same time, diphenylamine is replaced by carbazole to obtain complexes (R)-j1 and (S)-j1.

[0087] Example 11 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0088] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is as follows: the compound represented by formula C3 is prepared according to the preparation method of Example 3. Subsequently, the preparation method of Example 2 is followed, and the compound represented by formula C2 in Example 2 is replaced by the compound represented by formula C3 to obtain complexes (R)-k1 and (S)-k1.

[0089] Example 12 The structural formula of the circularly polarized phosphorescent Pt(II) complex is: .

[0090] Refer to the attached Figure 1 The preparation method of the circularly polarized phosphorescent Pt(II) complex is carried out according to the preparation method of Example 12. At the same time, the di(mesityl)boron fluoride in Example 12 is replaced by 2-chloro-4, 6-diphenyl 1,3,5-triazine to obtain complexes (R)-l1 and (S)-l1.

[0091] The circular dichroism spectra and circular polarization spectra of the corresponding complex enantiomers in dichloromethane solution were measured by circular dichroism spectrometer and circular polarization fluorescence spectrometer, and the corresponding g cd and g lum value.

[0092] Table 1 Circularly polarized luminescence properties of target chiral phosphorescent Pt(II) complexes Note: The complex is the target chiral phosphorescent Pt(II) complex, which is a pair of racemates. g cd represents the absorption asymmetry factor; g lum Indicates a high asymmetry factor.

[0093] from Figure 2 It can be seen from the circular dichroism spectrum that the enantiomers show obvious circular dichroism signals. And the enantiomers show higher luminescence asymmetry factors, among which the high asymmetry factor reaches g lum =1.2 10 -3 , the absorption asymmetry factor reaches g cd =1.7 10 -3 , and the quantum yield reaches Φ em =83.71%. This shows that the circularly polarized phosphorescent Pt(II) complex of the present invention has the beneficial effects of both high quantum yield and high asymmetry factor, and is of great research value for the development of circularly polarized chiral materials.

[0094] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A circularly polarized phosphorescent Pt(II) complex, characterized in that: It has a structure represented by the following formula (R)-I, formula (S)-I, formula (R)-II, formula (S)-II, formula (R)-III or formula (S)-III: ； Wherein, formula (R)-I and formula (S)-I are a pair of chiral enantiomers; formula (R)-II and formula (S)-II are a pair of chiral enantiomers; formula (R)-III and formula (S)-III are a pair of chiral enantiomers; the Ar group is an azaaryl group or a benzazaaryl group; -D(A) represents a group D or a group A; the group D represents an electron-rich donor group, and the group A represents an electron-deficient acceptor group; the group D is any one of a diphenylamine group and a carbazole group; and the group A is any one of a di(mesityl)boryl group and a 4,6-diphenyl-1,3,5-triazine-2-yl group.

2. The circularly polarized phosphorescent Pt(II) complex according to claim 1, characterized in that The Ar group is any one of a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a quinolyl group and an isoquinolyl group.

3. The circularly polarized phosphorescent Pt(II) complex according to claim 1, characterized in that The circularly polarized phosphorescent Pt(II) complex is selected from any one of the following compounds: 。 4. A method for preparing the circularly polarized phosphorescent Pt(II) complex according to any one of claims 1 to 3, characterized in that: The following steps are involved: Under an inert gas atmosphere, a halogen-substituted [2.2]-cyclophane is reacted with a 4-tri-n-butyltin-based Ar ring in the presence of lithium chloride, cuprous chloride, and a first palladium catalyst to undergo a C-C bond coupling reaction to obtain an Ar ring-substituted [2.2]-cyclophane; Under an inert gas atmosphere, the Ar ring-substituted [2.2]-cyclophane reacts with AX in the presence of n-butyl lithium to undergo a CC coupling reaction or a CB coupling reaction to obtain the Ar ring- and group-A-substituted [2.2]-cyclophane; the Ar ring and group-A-substituted [2.2]-cyclophane react in the presence of potassium chloroplatinite and sodium acetylacetonate to obtain a racemic circularly polarized phosphorescent Pt(II) complex; Alternatively, under an inert gas atmosphere, the Ar ring-substituted [2.2]-cyclophane is reacted with DH in the presence of a second palladium catalyst, a phosphine ligand, and a base to undergo a CN coupling reaction to obtain the Ar ring- and group-D-substituted [2.2]-cyclophane; the Ar ring- and group-D-substituted [2.2]-cyclophane is reacted in the presence of potassium chloroplatinite and sodium acetylacetonate to obtain a racemic circularly polarized phosphorescent Pt(II) complex; The racemic circularly polarized phosphorescent Pt(II) complex is separated by a high performance liquid phase chiral chromatography column to be split into chiral enantiomers to obtain a chiral circularly polarized phosphorescent Pt(II) complex; The specific reaction equation is as follows: ； The halogen-substituted [2.2]-cyclophane is a compound represented by formula IV-1, formula IV-2 or formula IV-3; the Ar ring of 4-tri-n-butyltin is Ar-SnBu3; X is a halogen; R1 and R2 are independently selected from halogens; the Ar ring-substituted [2.2]-cyclophane is a compound represented by formula V-1, formula V-2 or formula V-3; the Ar ring and group D(A)-substituted [2.2]-cyclophane is a compound represented by formula VI-1, formula VI-2 or formula VI-3; the racemic circularly polarized phosphorescent Pt(II) complex is a compound represented by formula (R / S)-I, formula (R / S)-II or formula (R / S)-III.

5. The method for preparing a circularly polarized phosphorescent Pt(II) complex according to claim 4, characterized in that: R1 and R2 are independently selected from I, F or Br; X is F.

6. The method for preparing a circularly polarized phosphorescent Pt(II) complex according to claim 4, characterized in that: The first palladium catalyst is tetrakistriphenylphosphine palladium; the second palladium catalyst is any one of palladium acetate, tetrakistriphenylphosphine palladium and tris(dibenzylideneacetone)dipalladium; The phosphine ligand is any one of tri-tert-butylphosphine, X-Phos, Ru-Phos and S-Phos; The base is any one of potassium carbonate, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide.

7. The method for preparing a circularly polarized phosphorescent Pt(II) complex according to claim 4, characterized in that: The molar ratio of the halogen-substituted [2.2] paracyclophane, 4-tri-n-butyltin-based Ar ring, lithium chloride, cuprous chloride and the first palladium catalyst is 1:1.2-1.5:1-1.5:1-1.5:0.02-0.05; The molar ratio of Ar ring-substituted [2.2] paracyclophane, AX and n-butyllithium is 1:1~1.5:1~1.2; The molar ratio of the Ar ring-substituted [2.2] paracyclophane, DH, the second palladium catalyst, the phosphine ligand and the base is 1:1.2~1.5:0.02~0.05:0.06~0.15:2~3; The molar ratio of the Ar ring and the [2.2]-cyclophane substituted with the group D(A), potassium chloroplatinite and sodium acetylacetonate is 1.05~1.2:1:2.2~2.

5.

8. The method for preparing a circularly polarized phosphorescent Pt(II) complex according to claim 4, characterized in that: In the process of preparing Ar-ring substituted [2.2]-cyclophane, the first solvent is N,N-dimethylformamide, the reaction temperature is 100°C, and the reaction time is 16 hours; In the process of preparing [2.2]-cyclophane substituted with Ar ring and group A, the second solvent is tetrahydrofuran, the reaction temperature is room temperature, and the reaction time is 16 h; In the process of preparing [2.2]-cyclophane substituted with Ar ring and group D, the third solvent is N,N-dimethylformamide, the reaction temperature is 120°C, and the reaction time is 16 hours; In the process of preparing a racemic circularly polarized phosphorescent Pt(II) complex, the fourth solvent is a mixed solution of ethylene glycol ethyl ether and water, and the volume ratio of ethylene glycol ethyl ether to water is 2.5~3.5:1, the reaction temperature is 60℃~75℃, and the reaction time is 1.5h~2h.

9. The method for preparing a circularly polarized phosphorescent Pt(II) complex according to claim 4, characterized in that: The inert gas is any one of nitrogen and argon.

10. Use of the circularly polarized phosphorescent Pt(II) complex according to any one of claims 1 to 3 as a circularly polarized luminescent material.

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