CN111793095A - Preparation method and application of cyclometalated platinum complex - Google Patents

Preparation method and application of cyclometalated platinum complex Download PDF

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CN111793095A
CN111793095A CN202010803853.4A CN202010803853A CN111793095A CN 111793095 A CN111793095 A CN 111793095A CN 202010803853 A CN202010803853 A CN 202010803853A CN 111793095 A CN111793095 A CN 111793095A
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刘春�
于凯旋
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Abstract

A preparation method and application of a cyclometalated platinum complex, which belongs to the field of phosphorescent materials. The invention synthesizes seven platinum complexes by taking 2-phenylpyridine and derivatives thereof as a ring metal ligand and 1, 10-phenanthroline and derivatives thereof as auxiliary ligands. The platinum complex prepared by the invention has obvious aggregation-induced emission property and has important application value in the field of phosphorescent materials.

Description

Preparation method and application of cyclometalated platinum complex
Technical Field
The invention relates to a preparation method and application of cyclometalated platinum complex with aggregation-induced emission property, belonging to the field of phosphorescent materials.
Background
Conventional fluorescent molecules typically have strong fluorescence in dilute solutions, and at high concentrations the fluorescence is reduced or even quenched. In 2001, Tang Benzhou et al discovered that an organic small molecule luminescent dye was substantially free of fluorescence in dilute solution and exhibited bright fluorescence Emission in the aggregated state (chem. Commun.,2001,18,1740-1741), which called Aggregation-Induced Emission (AIE for short). The discovery of aggregation-induced luminescence provides an effective idea for solving the important scientific problem of luminescence quenching caused by aggregation, and greatly promotes the application and development of high-efficiency solid-state luminescent materials. To date, the AIE molecules found in the literature are mostly purely organic small molecules, and relatively few materials based on novel Aggregation-Induced Phosphorescent Emission (AIPE) of transition metal complexes. Cyclometalated platinum complexes have been widely used in the fields of OLEDs (adv. optical Mater.,2020,8, 2000079; chem. Rec.,2019,19, 1693-. Therefore, the cyclometalated platinum complex which has excellent aggregation-induced emission property, simple structure and convenient preparation has important application value.
Disclosure of Invention
The invention aims to provide a preparation method of a cyclometalated platinum complex Pt1-Pt7 with aggregation-induced emission properties and the aggregation-induced emission properties thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the platinum complex Pt1-Pt7 comprises the following steps: synthesizing a ring metal ligand from 2, 5-dibromopyridine and phenylboronic acid or synthesizing an intermediate from 2-bromopyridine and phenylboronic acid derivatives as reactants, synthesizing the ring metal ligand from the intermediate, phenylboronic acid and derivatives thereof, coordinating with 1, 10-phenanthroline or derivatives thereof and platinum metal ions, and finally replacing anions to obtain the compound, wherein the compound has the following structure:
Figure BDA0002628381270000021
the preparation method of the cyclometalated ligand and platinum complex Pt1-Pt7 comprises the following specific synthetic steps:
(1) synthesis of cyclometalated ligand intermediate: adding 1.0mmol of 2-bromopyridine, a phenylboronic acid derivative (1.5equiv.), potassium carbonate (2.0equiv.), palladium acetate (1.5% equiv.) into a round-bottom flask in turn in air, then adding 8mL of ethanol-water mixed solution with the volume ratio of 3:1, carrying out magnetic stirring at 80 ℃ to carry out Suzuki cross-coupling reaction, tracking the reaction process by thin-layer chromatography, extracting with dichloromethane after the reaction is completed, merging organic phases, concentrating under reduced pressure, and carrying out column chromatography separation to obtain the cyclometalated intermediate.
(2) Synthesis of cyclometallated ligand: sequentially adding 1.0mmol of 2, 5-dibromopyridine or a ring metal ligand intermediate, phenylboronic acid and a derivative thereof (1.5equiv.), potassium carbonate (2.0equiv.), palladium acetate (1.5% equiv.) into a round-bottom flask in air, then adding 8mL of ethanol-water mixed solution with the volume ratio of 3:1, magnetically stirring at 80 ℃ to perform Suzuki cross-coupling reaction, tracking the reaction process by thin-layer chromatography, extracting with dichloromethane after the reaction is completed, combining organic phases, concentrating under reduced pressure, and separating by column chromatography to obtain a ring metal ligand;
(3) synthesis of platinum complex: to a round bottom two neck flask was added a ring metal ligand and 1.2 equivalents of potassium tetrachloroplatinate, N2Replacing for 3 times, adding 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution, reacting for 24 hours at 105 ℃ under the protection of nitrogen by magnetic stirring, transferring the reaction solution to a single-neck round-bottom flask after the reaction is finished, and performing vacuum concentration to obtain a dichloro bridge intermediate product; then 2.0 equivalent of 1, 10-phenanthroline or its derivative and 8mL of ethylene glycol monoethyl ether are added into the round-bottom flask, and the mixture is magnetically stirred at 105 ℃ for 24 hours under the nitrogen atmosphere. After the reaction was complete, the reaction mixture was cooled to room temperature and then 20mL of KPF was added6The saturated aqueous solution was stirred at room temperature for 2 h. After the reaction is finished, extracting by using dichloromethane, combining organic phases, and concentrating under reduced pressure to obtain a crude product; using dichloromethane/methanol as eluent, separating by column chromatography to obtain target product, and making the product pass through1H NMR and high resolution mass spectrometry identification.
The platinum complex includes the following derivatives:
the complex Pt 1: the ring metal ligand is selected from 2- (3-phenyl) phenylpyridine, and the auxiliary ligand is selected from 1, 10-phenanthroline.
The complex Pt 2: the ring metal ligand is selected from 2- (2-phenyl) phenylpyridine, and the auxiliary ligand is selected from 1, 10-phenanthroline.
The complex Pt 3: the ring metal ligand is selected from 2, 5-diphenylpyridine, and the auxiliary ligand is selected from 1, 10-phenanthroline.
The complex Pt 4: the ring metal ligand is selected from 2- (4-biphenyl) phenylpyridine, and the auxiliary ligand is selected from 1, 10-phenanthroline.
The complex Pt 5: the ring metal ligand is selected from 2-phenylpyridine, and the auxiliary ligand is selected from 4, 7-diphenyl-1, 10-phenanthroline.
The complex Pt 6: the ring metal ligand is selected from 2- (4-biphenyl) pyridine, and the auxiliary ligand is selected from 4, 7-diphenyl-1, 10-phenanthroline.
The complex Pt 7: the ring metal ligand is selected from 2, 5-diphenylpyridine, and the auxiliary ligand is selected from 4, 7-diphenyl-1, 10-phenanthroline.
The invention has the beneficial effects that:
1. the method for synthesizing the ring metal ligand by the Suzuki cross-coupling reaction is environment-friendly, simple, convenient and efficient.
2. The platinum complex with excellent aggregation-induced emission property can be obtained by introducing the cyclometalated platinum complex with the freely rotatable benzene ring through modular design.
3. In the mixed solution of the complex Pt1-Pt7 and the water content of the poor solvent is increased, the complex emits very weak light at the beginning, and the emission intensity reaches the highest when the water content is 70-90%. The result shows that the complex Pt1-Pt7 has excellent aggregation-induced emission property.
Drawings
FIG. 1 is a graph of the emission spectrum of the complex Pt1 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 2 is an emission spectrum of the complex Pt2 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 3 is an emission spectrum of the complex Pt3 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 4 is an emission spectrum of the complex Pt4 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 5 is an emission spectrum of the complex Pt5 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 6 is an emission spectrum of the complex Pt6 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
FIG. 7 is an emission spectrum of the complex Pt7 at different water contents (the solvent is acetonitrile/water, 5X 10)-5mol/L)。
Detailed Description
Example 1 Synthesis of Complex Pt1
(1) Synthesis of cyclometalated ligand intermediate:
adding 1.0mmol of 2-bromopyridine, 1.5equiv of 3-bromobenzoic acid, 2.0equiv of potassium carbonate and 1.5 percent of palladium acetate into a round-bottom flask in turn in the air, then adding 8mL of ethanol-water mixed solution with the volume ratio of 3:1, magnetically stirring at 80 ℃ to carry out Suzuki cross-coupling reaction, tracking the reaction process by thin-layer chromatography, adding 20mL of saturated saline after the reaction is completed, extracting by dichloromethane, combining organic phases, concentrating under reduced pressure, and separating by column chromatography to obtain the cyclometal ligand intermediate.
(2) Synthesis of cyclometallated ligand:
sequentially adding 1.0mmol of a ring metal ligand intermediate, phenylboronic acid (1.5equiv.), potassium carbonate (2.0equiv.), palladium acetate (1.5% equiv.) into a round-bottom flask in air, then adding 8mL of ethanol-water mixed solution with the volume ratio of 3:1, carrying out Suzuki cross-coupling reaction by magnetic stirring at 80 ℃, tracking the reaction process by thin-layer chromatography, adding 20mL of saturated saline after the reaction is completed, extracting with dichloromethane, combining organic phases, concentrating under reduced pressure, and separating by column chromatography to obtain the ring metal ligand;
(3) synthesis of platinum complex:
to a round bottom two neck flask was added a ring metal ligand and 1.2 equivalents of potassium tetrachloroplatinate, N2And (3) replacing for 3 times, adding 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution, reacting for 24 hours at 105 ℃ under the protection of nitrogen by magnetic stirring, transferring the reaction solution into a single-neck round-bottom flask after the reaction is finished, and carrying out vacuum rotary evaporation to obtain a dichloro bridge intermediate product. Then 2.0 equivalent of 1, 10-phenanthroline and 8mL of ethylene glycol monoethyl ether are added, and the mixture is magnetically stirred and reacted for 24 hours at 105 ℃ in the nitrogen atmosphere. After the reaction was complete, the reaction mixture was cooled to room temperature and then 20mL of KPF was added6The saturated aqueous solution was stirred at room temperature for 2 h. After the reaction is finished, extracting by using dichloromethane, combining organic phases, and concentrating under reduced pressure to obtain a crude product; the target product is obtained by column chromatography separation with dichloromethane/methanol as eluent, and the yield is 74%. The structural characterization data is as follows:1H NMR(400MHz,DMSO-d6)9.37(d,J＝4.0Hz,1H),9.10(s,1H),8.59(dd,J＝15.5,7.9Hz,3H),7.98(s,2H),7.87(s,1H),7.81–7.61(m,5H) 7.54(t, J ═ 7.5Hz,2H),7.44(t, J ═ 7.2Hz,1H),7.37(s,1H),7.09(m,3H), HRMS (LTQ, m/z): calculated value C29H20F6N3PPt[M-PF6]+605.1305, found 605.1279.
Example 2 Synthesis of Complex Pt2
Example 2 was prepared identically to example 1, except that: the phenylboronic acid derivative used in the synthesis of the cyclic metal ligand intermediate of example 2 was 2-bromobenzeneboronic acid.
Pt2 yield 43%, structural characterization data are as follows:1H NMR(400MHz,DMSO-d6)9.68(d, J ═ 4.2Hz,1H),9.37(d, J ═ 4.0Hz,1H),9.00(d, J ═ 8.1Hz,2H),8.90(d, J ═ 5.3Hz,1H),8.27(d, J ═ 3.3Hz,3H),8.02(s,1H), 7.64-7.46 (m,4H),7.38(dd, J ═ 17.1,6.8Hz,3H),7.23(s,1H),7.12(s,1H),6.99(d, J ═ 7.3Hz,1H),6.35(d, J ═ 8.2Hz,1H), HRMS (LTQ, m/z): calculated value C29H20F6N3PPt[M-PF6]+605.1305, found 605.1284.
Example 3 Synthesis of Complex Pt3
(1) Synthesis of cyclometallated ligand:
adding 1.0mmol of 2, 5-dibromopyridine, 1.5equiv of phenylboronic acid, 2.0equiv of potassium carbonate and 1.5% equiv of palladium acetate into a round-bottomed flask in turn in air, then adding 8mL of ethanol-water mixed solution with the volume ratio of 3:1, carrying out Suzuki cross-coupling reaction by magnetic stirring at 80 ℃, tracking the reaction process by thin-layer chromatography, adding 20mL of saturated saline solution after the reaction is completed, extracting with dichloromethane, combining organic phases, concentrating under reduced pressure, and separating by column chromatography to obtain a ring metal ligand;
(2) synthesis of platinum complex:
to a round bottom two neck flask was added a ring metal ligand and 1.2 equivalents of potassium tetrachloroplatinate, N2And (3) replacing for 3 times, adding 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution, reacting for 24 hours at 105 ℃ under the protection of nitrogen by magnetic stirring, transferring the reaction solution into a single-neck round-bottom flask after the reaction is finished, and carrying out vacuum rotary evaporation to obtain a dichloro bridge intermediate product. Then 2.0 equivalent of 1, 10-phenanthroline and 8mL of ethylene glycol monoethyl ether are addedEther, under nitrogen atmosphere, was reacted at 105 ℃ with magnetic stirring for 24 h. After the reaction was complete, the reaction mixture was cooled to room temperature and then 20mL of KPF was added6The saturated aqueous solution was stirred at room temperature for 2 h. After the reaction is finished, extracting by using dichloromethane, combining organic phases, and concentrating under reduced pressure to obtain a crude product; the target product is obtained by column chromatography separation and purification with dichloromethane/methanol as eluent, and the yield is 41%. The structural characterization data is as follows:1H NMR(400MHz,DMSO-d6)9.49(s,1H),9.28(s,1H),8.92(d, J ═ 7.4Hz,1H),8.82(d, J ═ 7.2Hz,1H),8.74(s,1H),8.25(s,3H),8.03(s,1H),7.90(s,1H),7.77(dd, J ═ 19.7,7.8Hz,3H),7.56(m,3H),7.32(d, J ═ 6.5Hz,1H),7.14(d, J ═ 6.8Hz,1H),6.96(t, J ═ 6.2Hz,2H), HRMS (LTQ), m/z calculated value C/z29H20F6N3PPt[M-PF6]+605.1305, found 605.1298.
Example 4 Synthesis of Complex Pt4
Example 4 was prepared identically to example 1, except that: the phenylboronic acid derivative used in the synthesis of the cyclic metal ligand intermediate of example 4 was 4-bromobenzeneboronic acid; the phenylboronic acid derivative used in the synthesis of the ring metal ligand is 4-biphenylboronic acid.
Yield of Pt4 was 48%. The structural characterization data is as follows:1H NMR(400MHz,DMSO-d6)9.50(s,1H),9.24(s,1H),8.73(m,3H), 8.20-8.09 (m,2H),7.92(d, J ═ 6.9Hz,2H), 7.82-7.61 (m,8H), 7.54-7.39 (m,3H), 7.34-7.09 (m,4H), HRMS (LTQ, m/z): calculated C: calculated35H24F6N3PPt[M-PF6]+681.1618, found 681.1616.
Example 5 Synthesis of Complex Pt5
(1) Synthesis of platinum complex:
to a round bottom two neck flask was added 0.2mmol of 2-phenylpyridine and 1.2 equivalents of potassium tetrachloroplatinate, N2And (3) replacing for 3 times, adding 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution, reacting for 24 hours at 105 ℃ under the protection of nitrogen by magnetic stirring, transferring the reaction solution into a single-neck round-bottom flask after the reaction is finished, and carrying out vacuum rotary evaporation to obtain a dichloro bridge intermediate product. Then 2.0 equivalent of 4, 7-diphenyl-1, 10-phenanthroline and 8mL of ethylene glycol are addedThe alcohol monoethyl ether is reacted for 24 hours under nitrogen atmosphere and magnetic stirring at 105 ℃. After the reaction was complete, the reaction mixture was cooled to room temperature and then 20mL of KPF was added6The saturated aqueous solution was stirred at room temperature for 2 h. After the reaction is finished, extracting by using dichloromethane, combining organic phases, and concentrating under reduced pressure to obtain a crude product; the target product is obtained by column chromatography separation and purification with dichloromethane/methanol as eluent, and the yield is 49%. The structural characterization data is as follows:1H NMR(400MHz,DMSO-d6)9.61(s,1H),9.31(s,1H),8.79(s,1H),8.07(s,2H),7.93(s,1H),7.74(t, J ═ 14.2Hz,12H),7.53(s,1H),7.31(s,1H),7.16(s,2H),7.02(s,1H),6.81(s,1H). HRMS (LTQ, m/z): calculated value C, 1H, H35H24F6N3PPt[M-PF6]+681.1618, found 681.1610.
Example 6 Synthesis of Complex Pt6
Example 6 was prepared identically to example 1, except that: the phenylboronic acid derivative used in the synthesis of the cyclic metal intermediate of example 6 was 4-bromobenzeneboronic acid; the 1, 10-phenanthroline derivative used in the synthesis of the platinum complex is 4, 7-diphenyl-1, 10-phenanthroline.
Yield of Pt6 was 34%, and structural characterization data were as follows:1H NMR(400MHz,DMSO-d6)9.66(s,1H),9.31(s,1H),8.73(s,1H),8.11(d, J ═ 6.9Hz,2H), 7.94-7.30 (m,20H), 7.28-7.06 (m,2H),6.92(s,1H). HRMS (LTQ, m/z): calcd for C41H28F6N3PPt[M-PF6]+757.1931, found 757.1908.
Example 7 Synthesis of Complex Pt7
Example 7 was prepared identically to example 3, except that: the 1, 10-phenanthroline derivative used in the synthesis of the platinum complex in example 7 is 4, 7-diphenyl-1, 10-phenanthroline.
Pt7 yield 67%, structural characterization data are as follows:1H NMR(400MHz,DMSO-d6)9.57(s,1H),9.34(s,1H),8.82(s,1H),8.16(d, J ═ 9.8Hz,2H),8.00(s,2H),7.77(m,7H),7.65(m,7H),7.53(s,3H),7.23(s,2H),7.05(s,1H),6.80(s,1H). HRMS (LTQ, m/z): calculated value C, 1H, H41H28F6N3PPt[M-PF6]+757.1931, found 757.1934.
EXAMPLE 8 AIE Property testing of Complex Pt1-Pt7
The complex Pt1-Pt7 is dissolved in acetonitrile to be prepared into a concentration of 5X 10-4mixing the sample solution dissolved with acetonitrile, acetonitrile and water according to different volume ratios to form mixed solutions (with concentration of 5 × 10) with different water contents- 5mol/L), followed by bubbling with nitrogen for 3 minutes and testing the emission spectrum. The results of FIGS. 1 to 7 show that in the acetonitrile/water mixed solution, the complex emits very weak light at the beginning with an increase in the water content of the poor solvent, and the emission intensity reaches the highest by the water content of 70% to 90%. The result shows that the complex Pt1-Pt7 has excellent aggregation-induced emission property.

Claims (3)

1. A cyclometalated platinum complex is characterized in that: the platinum complex is formed by coordination of 2-phenylpyridine and derivatives thereof serving as a ring metal ligand, 1, 10-phenanthroline and derivatives thereof serving as auxiliary ligands and platinum metal ions, and has the following structure:
Figure FDA0002628381260000011
the 2-phenylpyridine derivative is selected from 2- (3-phenyl) phenylpyridine, 2- (2-phenyl) phenylpyridine, 2, 5-diphenylpyridine, 2- (4-biphenyl) phenylpyridine and 2- (4-biphenyl) pyridine; the 1, 10-phenanthroline derivative is 4, 7-diphenyl-1, 10-phenanthroline.
2. The process for preparing a cyclometalated platinum complex according to claim 1, wherein: the synthesis steps of the platinum complex are as follows:
(1) synthesis of cyclometalated ligand intermediate: taking 2-bromopyridine and a phenylboronic acid derivative as reactants, potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in air at 80 ℃, tracking the reaction process by using a thin-layer chromatography, and after the reaction is completed, carrying out column chromatography separation to obtain a ring metal ligand intermediate;
(2) synthesis of cyclometallated ligand: taking 2, 5-dibromopyridine or a ring metal ligand intermediate and phenylboronic acid and a derivative thereof as reactants, potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in air at 80 ℃, tracking the reaction process by using a thin-layer chromatography, and after the reaction is completed, carrying out column chromatography separation to obtain a ring metal ligand;
(3) synthesis of platinum complex: to a round bottom two neck flask was added a ring metal ligand and 1.2 equivalents of potassium tetrachloroplatinate, N2Replacing for 3 times, adding 8mL of ethylene glycol monoethyl ether/water mixed solution with the volume ratio of 3:1, and reacting for 24 hours under the protection of nitrogen and magnetic stirring at 105 ℃; after the reaction is finished, transferring the reaction solution into a single-mouth round-bottom flask, and carrying out vacuum concentration to obtain a dichloro bridge intermediate product; then 2.0 equivalent of 1, 10-phenanthroline or a derivative thereof and 8mL of ethylene glycol monoethyl ether are added into the reaction bottle, and the mixture is magnetically stirred and reacted for 24 hours at 105 ℃ in the nitrogen atmosphere; after the reaction was complete, the reaction mixture was cooled to room temperature and then 20mL of KPF was added6Stirring the saturated aqueous solution at room temperature for 2 hours; after the reaction is finished, extracting with dichloromethane, and carrying out reduced pressure concentration on the collected organic phase to obtain a crude product; using dichloromethane/methanol as eluent, and obtaining the target product through column chromatography separation.
3. The use of a class of cyclometalated platinum complexes as claimed in claim 1, wherein: the cyclometalated platinum complex is applied to the field of phosphorescent materials.
CN202010803853.4A 2020-08-11 2020-08-11 Preparation method and application of cyclometalated platinum complex Pending CN111793095A (en)

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CN114106058B (en) * 2021-12-15 2023-09-12 大连理工大学 Preparation method and application of aggregation-induced emission platinum complex
CN114835706A (en) * 2022-05-11 2022-08-02 昆明理工大学 N ^ N ligand and application thereof
CN114835706B (en) * 2022-05-11 2023-10-27 昆明理工大学 N≡N ligand and application thereof

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Application publication date: 20201020