Circularly polarized phosphorescent Pt (II) complex based on pinene modification

Abstract

The circularly polarized phosphorescent Pt (II) complex based on pinene modification is characterized in that a pinene group and an azole group are connected to form the Pt (II) complex with a symmetric and asymmetric structure, and the chemical general formula of the Pt (II) complex is shown as follows: # imgabs0 # provides a chiral center due to the pinene group, and utilizes the characteristics of large steric hindrance and chirality of pinene micromolecules to induce spiral accumulation of the Pt (II) complex, so that the pinene micromolecules can be converted into pinene micromolecules, and the pinene micromolecules can be converted into pinene micromolecules, so that the pinene micromolecules can be converted into pinene micromolecules, and the pinene micromolecules can be converted into pinene micromolecules. Therefore, plane rigidity and circular polarization characteristics are considered, chiral signals and quantum yield of a system are enhanced, and the compound shows excellent luminescence performance in dark red light and has great development prospects in the field of photoelectric materials.

Description

Technical Field

[0001] The invention relates to the technical field of luminescent materials, and in particular to a type of circularly polarized phosphorescent Pt(II) complexes modified with pinene. Background Art

[0002] Circularly polarized luminescence (CPL) originates from chiral excited states, which refers to the phenomenon that chiral substances (or chiral luminescent systems) emit left-handed or right-handed circularly polarized light under the excitation of light. In recent years, CPL materials have great application prospects in high-tech fields such as 3D display, biological probes, quantum communications, and new anti-counterfeiting, so the design and synthesis of chiral functional materials has important research significance.

[0003] Early research on CPL luminescent materials mainly focused on rare earth complexes, because their unique magnetically allowed transitions can obtain higher luminescence asymmetry factors, but they usually need to rely on the antenna effect of organic chromophores to promote luminescence, with low luminescence efficiency and limited device brightness, which to a certain extent limits their application in the optoelectronic field. In 2021, Lin Lirong's research group at Xiamen University reported four β-diketone-chiral bipyridine-rare earth complexes with chiral pinenyl bipyridine molecules (R / SL) as ligands in the study of the synthesis and circularly polarized luminescence and photoluminescence of homochiral β-diketone rare earth complexes. Among them, the complex [Eu(SL)(tta)3] has the highest asymmetry factor, g lum =-0.0145, and its luminescence quantum yield is 40.15% in acetonitrile solution. The low luminescence quantum efficiency limits the practical application of this type of material in the field of OLED.

[0004] For phosphorescent CPL materials that introduce transition metal atoms, due to the spin-orbit coupling of transition metal atoms, the energy of singlet and triplet states can be used simultaneously, and the internal quantum efficiency can reach 100% in theory, thus obtaining optoelectronic devices with high luminescence efficiency. Therefore, transition metal complexes with circularly polarized phosphorescent activity will have more prominent advantages in the field of new luminescence, but there are few research results with higher luminescence asymmetry factor and quantum yield at the same time. Summary of the invention

[0005] In order to overcome the defects of the above-mentioned prior art, the purpose of the present invention is to provide a type of circularly polarized phosphorescent Pt(II) complex modified based on pinene, in which the chiral center is provided by the pinene group, and the characteristics of pinene small molecules with large steric hindrance and chirality are utilized to induce helical stacking of the Pt(II) complex, enhance the chiral signal and quantum yield of the system, so as to obtain a new Pt(II) complex structure molecule with simple structure and easy synthesis.

[0006] To achieve the above object, the technical solution of the present invention is:

[0007] The circularly polarized phosphorescent Pt(II) complex modified with pinene has the following general chemical formula:

[0008]

[0009] In the above formula, the substituent G is selected from one of the following: trifluoromethyl, pentafluoroethyl, cyano group or methyl, ethyl, tert-butyl, straight chain or branched alkyl group with less than 6 carbon atoms;

[0010] Ar1 is selected from one of the following: a five-membered nitrogen heterocyclic ring of thiazole, imidazole, pyrazole, pyrrole, 1,2,3-triazole or 1,2,4-triazole;

[0011] Ar2 is selected from one of the following: a six-membered nitrogen heterocyclic ring of pyridine, pyrazine, pyrimidine, quinoline or isoquinoline;

[0012] Ar3 is selected from the following nitrogen heterocycles: pyridine, pyrazine, pyrimidine, quinoline, isoquinoline, thiazole, benzothiazole, benzopyrazole;

[0013] Ar4 is selected from the following: benzene, substituted benzene, thiophene, pyridine, carbazole, fluorene, benzothiophene monocyclic ring and condensed aromatic ring;

[0014] Ar5 is selected from one of the following: a five-membered nitrogen heterocyclic ring of thiazole, imidazole, pyrazole, pyrrole, 1,2,3-triazole or 1,2,4-triazole;

[0015] Ar6 is selected from one of the following: a six-membered nitrogen heterocyclic ring of pyridine, pyrazine, pyrimidine, quinoline or isoquinoline.

[0016] The circularly polarized phosphorescent Pt(II) complex modified with pinene specifically comprises the following structure:

[0017]

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) The present invention connects a unique pinene group with circular polarization properties with an azole group to synthesize a C^N organic ligand, and at the same time utilizes the advantages of the Pt(II) complex, such as the four-coordinate planar structure, high exciton utilization rate, and adjustable color, to obtain a highly efficient phosphorescent Pt(II) complex that takes into account both the luminescence quantum yield and circular polarization properties, providing a new idea for the molecular design of circularly polarized phosphorescent materials.

[0020] (2) The present invention utilizes the spatial characteristics of the pinene group with large steric hindrance to limit molecular distortion, thereby further improving the luminescence efficiency of the complex; and because the steric hindrance of the unilateral chiral pinene group is moderate, it can induce the planar cyclometallated Pt(II) complex to undergo spiral stacking, forming chiral spiral self-assembled aggregates, greatly enhancing the chiral signal of the system.

[0021] (3) The circularly polarized phosphorescent Pt(II) complex modified with pinene designed in the present invention realizes deep red light emission with a maximum emission wavelength of 665 nm. lum Reaching 0.0049, and the quantum yield is as high as 67.8%, with high Φ em and high g lum The beneficial effects are of great research value for the development of circularly polarized chiral materials.

[0022] In summary, the Pt(II) complex of the present invention, which is formed by connecting the pinene group and the azole group and has a symmetrical and asymmetrical structure, takes into account both planar rigidity and circular polarization properties, and can exhibit excellent luminescence performance in deep red light, and has great development prospects in the field of optoelectronic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the synthetic route for preparing the target Pt(II) complex of the present invention.

[0024] Figure 2 This is the steady-state spectrum diagram of the target Pt(II) complex provided by the present invention. DETAILED DESCRIPTION

[0025] To explain the circularly polarized phosphorescent Pt(II) complex modified with pinene in detail, the present invention is described in detail below with reference to the examples.

[0026] The present invention discloses a circularly polarized phosphorescent Pt(II) complex modified with pinene, and the general chemical formula thereof is as follows:

[0027]

[0028] The complex described by the chemical formula can be prepared by the following method, comprising the following steps:

[0029] Step 1: Synthesize organic intermediate A1 or B1 containing azole groups, specifically:

[0030] (1) 3-Butyne-2-one, 2,2,2-trifluoroethylamine and tert-butyl nitrite are dissolved in a mixed solution of dichloromethane and glacial acetic acid, and the reaction mixture is reacted at 0-5°C for 1 hour, and then continued to react at 60-65°C for 10-12 hours. After the reaction is completed, the mixture is cooled to room temperature and poured into water, extracted three times with dichloromethane, and the organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is separated by column chromatography to obtain intermediate A1.

[0031] (2) 3-Butyne-2-one, aminoacetonitrile hydrochloride and sodium nitrite are dissolved in a mixed solution of chloroform and water, and the reaction mixture is reacted at 0-5°C for 1 hour, and then continued to react at 25-30°C for 10-12 hours. After the reaction is completed, the mixture is cooled to room temperature and poured into water, extracted three times with dichloromethane, and the organic phase is dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a crude product, which is separated by column chromatography to obtain intermediate B1.

[0032] Among them, the molar ratio of 3-butyne-2-one, 2,2,2-trifluoroethylamine and tert-butyl nitrite is preferably 1:2-3:2.1-2.6, and the volume ratio of the mixed solution of dichloromethane and glacial acetic acid is 10-15:1. The molar ratio of 3-butyne-2-one, aminoacetonitrile hydrochloride and sodium nitrite is preferably 1:2-2.5:3-3.5, and the volume ratio of the mixed solution of chloroform and water is 10-15:1.

[0033] Step 2: Synthesize organic intermediate A2 or B2 containing bromoazole groups, specifically:

[0034] Under an inert gas atmosphere, the organic intermediate A1 or B1 obtained in step 2 and tribromopyridinium salt are dissolved in a mixed solution of tetrahydrofuran and methanol, heated to 50-55°C for reaction for 10-12h, cooled to room temperature after the reaction, poured into water, 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 to obtain intermediate A2 or B2.

[0035] Among them, the molar ratio of A1 or B1 to tribromopyridinium salt is preferably 1:1.5-2, and the volume ratio of the mixed solution of tetrahydrofuran and methanol is 4-5:1.

[0036] Step 3: Synthesize the pyridinium salt compound A3 or B3 containing an azole group, specifically:

[0037] Under an inert gas atmosphere, the organic intermediate A2 or B2 obtained in step 3 is dissolved in a mixed solution of pyridine and acetone, heated to 60-65°C for reaction for 6-7 hours. After the reaction is completed, the temperature is cooled to room temperature, and ethanol is added to obtain a solid crude product A3 or B3, which is directly used in the next reaction.

[0038] The preferred molar ratio of A2 or B2 to pyridine is 1:1.5-2.

[0039] Step 4: Synthesize an organic ligand containing a pinene group, specifically:

[0040] Under an inert gas atmosphere, the organic intermediate A3 or B3 obtained in step 4, myrtle aldehyde (R or S) and ammonium acetate are dissolved in an ethanol solution and heated to 80-85°C for 10-12 hours. After the reaction is completed, the mixture is cooled to room temperature and poured into water, extracted three times with dichloromethane, the organic phase is dried over anhydrous sodium sulfate, and vacuum concentrated to obtain a crude product, which is separated by column chromatography to obtain L1-R, L1-S, L2-R or L2-S.

[0041] Among them, the preferred molar ratio of A3 or B3, myrtle aldehyde (R or S) and ammonium acetate is 1:1-1.5:2-3.

[0042] Step 5: Synthesizing a chiral phosphorescent Pt(II) complex containing a pinene group, specifically:

[0043] (1) Under an inert gas atmosphere, L1-R, L1-S, L2-R or L2-S, PtCl(DMSO)PPY and sodium acetate are dissolved in glacial acetic acid solution, and the mixture is heated to 115-120°C for reaction for 10-12h. After the reaction system is cooled to room temperature, it is extracted three times with dichloromethane, the organic phase is dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum. The crude product is separated and purified by column chromatography to obtain the target chiral phosphorescent Pt(II) complex 1-R, 1-S, 3-R or 3-S.

[0044] (2) Under an inert gas atmosphere, L1-R, L1-S, L2-R or L2-S, PtCl2(DMSO)2 and sodium carbonate are dissolved in tetrahydrofuran solution, and the mixture is heated to 65-70°C for reaction for 10-12 hours. After the reaction system is cooled to room temperature, it is extracted three times with dichloromethane, the organic phase is dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum conditions. A solid crude product is obtained, and the target chiral phosphorescent Pt(II) complex 2-R, 2-S, 4-R or 4-S is obtained by washing with dichloromethane three times.

[0045] Wherein, the inert gas is preferably any one of nitrogen and argon.

[0046] Preferably, the molar ratio of L1-R, L1-S, L2-R or L2-S, PtCl(DMSO)PPY and sodium acetate is 1:1.0-1.2:3.0-3.5, and preferably, the molar ratio of L1-R, L1-S, L2-R or L2-S, PtCl2(DMSO)2 and sodium carbonate is 2-2.2:1:3.0-3.5.

[0047] The following embodiments are only preferred embodiments of the present invention and do not limit the present invention. If necessary, the present invention may be modified and changed by those skilled in the art. All modifications and replacements made on the basis of the principles and spirit of the present invention should be included in the protection scope of the present invention.

[0048] Example 1

[0049] The target luminescent molecular structure of this embodiment is 1-R or 1-S:

[0050]

[0051] See attached Figure 1 , and its synthetic route comprises the following steps:

[0052] (1) 3-Butyne-2-ol (1.0 equiv.), 2,2,2-trifluoroethylamine (2.0 equiv.) and tert-butyl nitrite (2.4 equiv.) were dissolved in a mixed solution of dichloromethane (30 mL) and glacial acetic acid (2 mL). The temperature of the reaction system was controlled at 0°C for 1 h, and then the temperature was raised to 60°C for further reaction for 12 h. After the reaction was completed, the temperature was lowered to room temperature and poured into water, extracted three times with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target molecule A1 with a yield of 54%. 1 H NMR (400MHz, Chloroform-d) δ14.64(br,1H),7.52(s,1H),2.53(s,3H).

[0053] (2) Under nitrogen atmosphere, A1 (1.0 equiv.) and tribromopyridinium salt (2.0 equiv.) were dissolved in a mixed solution of tetrahydrofuran (5 mL) and methanol (1 mL), heated to 50°C for 12 h, cooled to room temperature after the reaction and poured into water, 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 to obtain intermediate A2 with a yield of 80%. It was directly used in the next step.

[0054] (3) Under nitrogen atmosphere, A2 (1.0 equiv.) was dissolved in pyridine (1.5 equiv.) and acetone (10 mL) in a mixed solution of pyridine and acetone, and heated to 60°C for 6 h. After the reaction, the mixture was cooled to room temperature and ethanol was added to obtain a solid crude product A3 with a yield of 94%. The product was directly used in the next reaction.

[0055] (4) Under nitrogen atmosphere, A3 (1.0 equiv.), myrtle aldehyde (R or S) (1.0 equiv.) and ammonium acetate (2.0 equiv.) were dissolved in ethanol (16 mL) and heated to 80°C for 12 h. 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 and concentrated in vacuo to obtain a crude product, which was separated by column chromatography to obtain L1-R or L1-S with a yield of 40%. L1-R: 1H NMR (400MHz, Chloroform-d): δ12.92(br,1H),8.18(s,1H),7.44(s,1H),6.89(s,1H),3.02(d,J=4.0Hz, 2H), 2.86 (t, J = 4.0Hz, 1H), 2.72 (m, 1H), 2.33 (m, 1H), 1.41 (s, 3H), 1.23 (d, J = 12.0Hz, 1H), 0.65 (s, 3H).

[0056] (5) Under nitrogen atmosphere, L1-R or L1-S (1.0 equiv.), PtCl(DMSO)PPY (1.0 equiv.) and sodium acetate (3.0 equiv.) were dissolved in glacial acetic acid (5 mL) solution, and the mixture was heated to 115°C for 12 h. After the reaction system was cooled to room temperature, it was extracted with dichloromethane, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target chiral phosphorescent Pt(II) complex 1-R or 1-S with a yield of 52%. Reference Figure 2 The emission wavelength of complex 1-R is 638nm, the luminescence quantum yield is 25.0%, g lum is 0.0037. Complex 1-R: 1 HNMR (400MHz, Chloroform-d): δ10.52(d,J=4.0Hz,1H),8.75(s,1H),8.21(s,1H),7.86(m,1H),7.68(d,J=8.0Hz,1H),7.55(d,J=4.0Hz,1H),7.45(d,J =4.0Hz,1H),7.29(m,2H),7.19(m,1H),3.11(s,2H),2.94(t,J=8.0Hz,1H), 2.80(m,1H),2.40(m,1H),1.46(s,3H),1.32(d,J=9.0Hz,1H),0.70(s,3H).

[0057] Example 2

[0058] The target luminescent molecular structure of this embodiment is 2-R or 2-S:

[0059]

[0060] See attached Figure 1 , and its synthetic route comprises the following steps:

[0061] 1) 3-Butyne-2-ol (1.0 equiv.), 2,2,2-trifluoroethylamine (2.0 equiv.) and tert-butyl nitrite (2.4 equiv.) were dissolved in a mixed solution of dichloromethane (30 mL) and glacial acetic acid (2 mL). The temperature of the reaction system was controlled at 5°C for 1 hour, and then the temperature was raised to 65°C for further reaction for 10 hours. After the reaction was completed, the temperature was lowered to room temperature and poured into water, extracted three times with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and then concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target molecule A1 with a yield of 52%. 1 H NMR (400MHz, Chloroform-d) δ14.64(br,1H),7.52(s,1H),2.53(s,3H).

[0062] 2) Under nitrogen atmosphere, A1 (1.0 equiv.) and tribromopyridinium salt (2.0 equiv.) were dissolved in a mixed solution of tetrahydrofuran (5 mL) and methanol (1 mL), heated to 55°C for 10 h, cooled to room temperature after the reaction and poured into water, 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 to obtain intermediate A2 with a yield of 82%. It was directly used in the next step.

[0063] 3) Under nitrogen atmosphere, A2 (1.0 equiv.) was dissolved in pyridine (1.5 equiv.) and acetone (10 mL) in a mixed solution of pyridine and acetone, and heated to 65°C for 7 h. After the reaction, the mixture was cooled to room temperature and ethanol was added to obtain a solid crude product A3 with a yield of 94%. The product was directly used in the next reaction.

[0064] 4) Under nitrogen atmosphere, A3 (1.0 equiv.), myrtle aldehyde (R or S) (1.0 equiv.) and ammonium acetate (2.0 equiv.) were dissolved in ethanol (16 mL) and heated to 85° C. for 10 h. 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 and concentrated in vacuo to obtain a crude product, which was separated by column chromatography to obtain L1-R or L1-S with a yield of 40%. L1-R: 1 H NMR (400MHz, Chloroform-d): δ12.92(br,1H),8.18(s,1H),7.44(s,1H),6.89(s,1H),3.02(d,J=4.0Hz, 2H), 2.86 (t, J = 4.0Hz, 1H), 2.72 (m, 1H), 2.33 (m, 1H), 1.41 (s, 3H), 1.23 (d, J = 12.0Hz, 1H), 0.65 (s, 3H).

[0065] 5) Under nitrogen atmosphere, L1-R or L1-S (2.0 equiv.), PtCl2(DMSO)2 (1.0 equiv.) and sodium carbonate (3.0 equiv.) were dissolved in tetrahydrofuran (5 mL) solution, and the mixture was heated to 65°C for 12 h. After the reaction system was cooled to room temperature, it was extracted with dichloromethane, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum. The solid crude product was washed three times with dichloromethane to obtain the target chiral phosphorescent Pt(II) complex 2-R or 2-S. Refer to the attached Figure 2 The emission wavelength of complex 2-R is 520nm, the luminescence quantum yield is 50.9%, g lum 0.0010. Complex 2-R: 1 H NMR (400MHz, Chloroform-d): δ9.76(d,J=8.0Hz,2H),7.12(d,J=8.0Hz,2H),6.48(d,J=8.0Hz,2H),3.16( d,J=8.0Hz,2H),2.97(d,J=8.0Hz,2H),2.83(m,4H),2.38(m,2H),1.46(s,6H),1.25(m,2H),0.64(s,6H).

[0066] Example 3

[0067] The target luminescent molecular structure of this embodiment is 3-R or 3-S:

[0068]

[0069] See attached Figure 1 , and its synthetic route comprises the following steps:

[0070] 1) Under nitrogen atmosphere, 3-butyne-2-ol (1.0 equiv.), aminoacetonitrile hydrochloride (2.0 equiv.) and sodium nitrite (3.0 equiv.) were dissolved in a mixed solution of chloroform (30 mL) and water (2 mL). The temperature of the reaction system was controlled at 0°C for 1 h, and then the temperature was raised to 25°C for further reaction for 12 h. After the reaction was completed, 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 and then concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target molecule B1 with a yield of 20%. 1 H NMR (400MHz, Chloroform-d) δ12.19(br,0.8H),7.19(s,1H),2.58(s,3H).

[0071] 2) Under nitrogen atmosphere, B1 (1.0 equiv.) and tribromopyridinium salt (2.0 equiv.) were dissolved in a mixed solution of tetrahydrofuran (5 mL) and methanol (1 mL), heated to 50°C for 12 h, cooled to room temperature after the reaction and poured into water, 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 to obtain intermediate B2 with a yield of 84%. It was directly used in the next step.

[0072] 3) Under nitrogen atmosphere, B2 (1.0 equiv.) was dissolved in pyridine (1.5 equiv.) and acetone (10 mL) in a mixed solution of pyridine and acetone, and heated to 60°C for 6 h. After the reaction, the mixture was cooled to room temperature and ethanol was added to obtain a solid crude product B3 with a yield of 95%. The product was directly used in the next reaction.

[0073] 4) Under nitrogen atmosphere, B3 (1.0 equiv.), myrtle aldehyde (R or S) (1.0 equiv.) and ammonium acetate (2.0 equiv.) were dissolved in ethanol (16 mL) and heated to 80°C for 12 h. 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 and concentrated in vacuo to obtain a crude product, which was separated by column chromatography to obtain L2-R or L2-S with a yield of 36%. L2-R: 1 H NMR (400MHz, Chloroform-d): δ12.32(br,1H),8.17(s,1H),7.41(s,1H),7.00(s,1H),3.04(d,J=4.0Hz, 2H), 2.88 (t, J = 4.0Hz, 1H), 2.74 (m, 1H), 2.35 (m, 1H), 1.43 (s, 3H), 1.23 (d, J = 12.0Hz, 1H), 0.66 (s, 3H).

[0074] 5) Under nitrogen atmosphere, L2-R or L2-S (1.0 equiv.), PtCl(DMSO)PPY (1.0 equiv.) and sodium acetate (3.0 equiv.) were dissolved in glacial acetic acid (5 mL) solution, and the mixture was heated to 115°C for 12 h. After the reaction system was cooled to room temperature, it was extracted three times with dichloromethane, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target chiral phosphorescent Pt(II) complex 3-R or 3-S with a yield of 55%. Refer to the attached Figure 2 The emission wavelength of complex 3-R is 665nm, the luminescence quantum yield is 67.8%, g lum is 0.0049. Complex 3-R: 1H NMR (400MHz, Chloroform-d): δ10.37 (d, J=8.0Hz, 1H), 8.72 (s, 1H), 8.09 (s, 1H) ,7.88(t,J=8.0Hz,1H),7.67(d,J=8.0Hz,1H),7.54(d,J=8.0Hz,1H),7.40(d,J= 8.0Hz,1H),7.29(s,1H),7.19(t,J=8.0Hz,1H),3.13(s,3H),2.96(t,J=8.0Hz,2 H), 2.83 (m, 1H), 2.42 (m, 1H), 1.47 (s, 3H), 1.37 (d, J = 12.0Hz, 1H), 0.72 (s, 3H).

[0075] Example 4

[0076] The target luminescent molecular structure of this embodiment is 4-R or 4-S:

[0077]

[0078] See attached Figure 1 , and its synthetic route comprises the following steps:

[0079] 1) Under nitrogen atmosphere, 3-butyne-2-ol (1.0 equiv.), aminoacetonitrile hydrochloride (2.0 equiv.) and sodium nitrite (3.0 equiv.) were dissolved in a mixed solution of chloroform (30 mL) and water (2 mL). The temperature of the reaction system was controlled at 5°C for 1 h, and then the temperature was raised to 30°C for further reaction for 10 h. After the reaction was completed, 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 and then concentrated under reduced pressure under vacuum. The crude product was separated and purified by column chromatography to obtain the target molecule B1 with a yield of 22%. 1 H NMR (400MHz, Chloroform-d) δ12.19(br,0.8H),7.19(s,1H),2.58(s,3H).

[0080] 2) Under nitrogen atmosphere, B1 (1.0 equiv.) and tribromopyridinium salt (2.0 equiv.) were dissolved in a mixed solution of tetrahydrofuran (5 mL) and methanol (1 mL), heated to 53°C for 11 h, cooled to room temperature after the reaction and poured into water, 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 to obtain intermediate B2 with a yield of 82%. It was directly used in the next step.

[0081] 3) Under nitrogen atmosphere, B2 (1.0 equiv.) was dissolved in pyridine (1.5 equiv.) and acetone (10 mL) in a mixed solution of pyridine and acetone, and heated to 63°C for 6.5 h. After the reaction, the mixture was cooled to room temperature and ethanol was added to obtain a solid crude product B3 with a yield of 91%. The product was directly used in the next reaction.

[0082] 4) Under nitrogen atmosphere, B3 (1.0 equiv.), myrtle aldehyde (R or S) (1.0 equiv.) and ammonium acetate (2.0 equiv.) were dissolved in ethanol (16 mL) and heated to 83°C for 11 h. 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 and concentrated in vacuo to obtain a crude product, which was separated by column chromatography to obtain L2-R or L2-S with a yield of 36%. L2-R: 1 H NMR (400MHz, Chloroform-d): δ12.32(br,1H),8.17(s,1H),7.41(s,1H),7.00(s,1H),3.04(d,J=4.0Hz, 2H), 2.88 (t, J = 4.0Hz, 1H), 2.74 (m, 1H), 2.35 (m, 1H), 1.43 (s, 3H), 1.23 (d, J = 12.0Hz, 1H), 0.66 (s, 3H).

[0083] 5) Under nitrogen atmosphere, L2-R or L2-S (2.0 equiv.), PtCl2(DMSO)2 (1.0 equiv.) and sodium carbonate (3.0 equiv.) were dissolved in tetrahydrofuran (5 mL) solution, and the mixture was heated to 62°C for 11 h. After the reaction system was cooled to room temperature, it was extracted three times with dichloromethane, the organic phase was dried over anhydrous Na2SO4, and concentrated under reduced pressure under vacuum. The solid crude product was washed three times with dichloromethane to obtain the target chiral phosphorescent Pt(II) complex 4-R or 4-S. Refer to the attached Figure 2 The emission wavelength of complex 4-R is 532nm, the luminescence quantum yield is 12.6%, g lum 0.0021. HRMS characterization data value: theoretical value 722.23139, experimental value 722.23305 [M+H] + .

[0084] Embodiment 5

[0085] The same synthesis method as in Example 1 or Example 3 is used, and the pyrazole raw material is replaced by a pyrazole derivative or a pyrrole derivative, and 2-phenylpyridine is replaced by 2-phenylpyrimidine, 2-phenylpyridine derivatives, 2-phenylisoquinoline derivatives or 3-pyridylfluorene derivatives to obtain complexes 5-R or 5-S, 7-R or 7-S, 9-R or 9-S, 11-R or 11-S. The photoluminescence and circular polarization properties of the obtained complexes are measured in the same manner, and the luminescence quantum yield can reach more than 45%, and the asymmetry factor g lum Can reach 10 -3 More than an order of magnitude.

[0086] Embodiment 6

[0087] The same synthesis method as in Example 2 or Example 4 is used, the pyrazole raw material is replaced by a triazole derivative or a pyrrole derivative, and the pyridine pinene group is replaced by a pyrimidine pinene group to obtain a complex 6-R or 6-S, 8-R or 8-S, 10-R or 10-S, 12-R or 12-S. The photoluminescence and circular polarization properties of the obtained complex are measured in the same manner, and the luminescence quantum yield can reach more than 40%, and the asymmetry factor g lum Can reach 10 -3 More than an order of magnitude.

Claims

1. A circularly polarized phosphorescent Pt(II) complex modified with pinene, characterized in that: Its general chemical formula is as follows: In the above formula, the substituent G is selected from one of the following: trifluoromethyl, pentafluoroethyl, cyano group or methyl, ethyl, tert-butyl, straight chain or branched alkyl group with less than 6 carbon atoms; Ar1 is selected from one of the following: a five-membered nitrogen heterocyclic ring of thiazole, imidazole, pyrazole, pyrrole, 1,2,3-triazole or 1,2,4-triazole; Ar2 is selected from one of the following: a six-membered nitrogen heterocyclic ring of pyridine, pyrazine, pyrimidine, quinoline or isoquinoline; Ar3 is selected from the following nitrogen heterocycles: pyridine, pyrazine, pyrimidine, quinoline, isoquinoline, thiazole, benzothiazole, benzopyrazole; Ar4 is selected from the following: benzene, substituted benzene, thiophene, pyridine, carbazole, fluorene, benzothiophene monocyclic ring and condensed aromatic ring; Ar5 is selected from one of the following: a five-membered nitrogen heterocyclic ring of thiazole, imidazole, pyrazole, pyrrole, 1,2,3-triazole or 1,2,4-triazole; Ar6 is selected from one of the following: a six-membered nitrogen heterocyclic ring of pyridine, pyrazine, pyrimidine, quinoline or isoquinoline.

2. The circularly polarized phosphorescent Pt(II) complex modified with pinene according to claim 1, characterized in that: Specifically includes the following structures:

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