阅读说明：本技术 一种二甲川胆色素类稀土配合物及其制备方法和应用 (Dimethylcholines rare earth complex and preparation method and application thereof ) 是由 宋森川 史华红 麦裕良 文武 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种二甲川胆色素类稀土配合物及其制备方法和应用,所述二甲川胆色素类稀土配合物的结构式为其中,所述R为吸电子基团,所述Ln为镧系元素。本发明的二甲川胆色素类稀土配合物可发出黄光和红光；且在长时间发光后发光强度下降程度低,具有良好的发光稳定性,在显示、照明领域具有很好的应用前景。本发明的制备方法具有步骤少、产物纯度高的优点,极大的降低了产品生产成本。(The invention discloses a dimethylchnane-type rare earth complex and a preparation method and application thereof, wherein the structural formula of the dimethylchnane-type rare earth complex is shown in the specification)

1. A dimethylchnane pigment rare earth complex is characterized in that: the dimethylcholines rare earth complex has a structural formula shown in formula 1:

wherein R is an electron-withdrawing group, and Ln is a lanthanide.

2. The dimethylcrochromin rare earth complex according to claim 1, wherein: and the R comprises at least one of trifluoromethyl, pentafluorophenyl, nitro and trihalomethyl.

3. A method for preparing dimethylchtanshin-class rare earth complex is characterized by comprising the following steps: the method comprises the following steps:

(1) dipyrromethene compoundsNucleophilic substitution reaction is carried out to prepare diacyl-substituted dipyrromethane compound

(2) Diacyl-substituted dipyrromethenesReacting with pyrrole to obtain dimethylochrolenin ligand

(3) Reacting a rare earth metal salt with a dimethobilin ligandReaction to generate dimethylchbile-class rare-earth complex

Wherein R is an electron-withdrawing group, and Ln is a lanthanide.

4. The method for producing the dimethylochronoid rare earth complex according to claim 3, which comprises: the step (1) is specifically that the dipyrromethane compound is mixed with a Grignard reagent for Grignard reaction, and then the acyl halide compound is addedCarrying out nucleophilic substitution reaction to generate diacyl-substituted dipyrromethane compound; the X represents halogen.

5. The method for producing the dimethylochronoid rare earth complex according to claim 4, which comprises: the step (1) is carried out under anhydrous condition.

6. The method for producing the dimethylochronoid rare earth complex according to claim 4, which comprises: in the step (1), the temperature of the Grignard reaction and the nucleophilic substitution reaction is independently 0-40 ℃.

7. The method for producing the dimethylochronoid rare earth complex according to claim 3, which comprises: the step (2) comprises the following more specific steps:

2-1) firstly, carrying out reduction reaction on a reducing agent and a diacyl-substituted dipyrromethane compound, and reducing carbonyl in the diacyl-substituted dipyrromethane compound into hydroxyl to obtain an intermediate 1;

2-2) then mixing the intermediate 1 with pyrrole, a catalyst, an oxidant and alkali, and reacting to generate the dimethylcholines ligand.

8. The method for producing the dimethylochronoid rare earth complex according to claim 7, which comprises: in the step 2-1), the temperature of the reduction reaction is 0-40 ℃;

preferably, in the step 2-1), the molar ratio of the reducing agent to the diacyl-substituted dipyrromethane compound is 50-55: 1;

preferably, in the step 2-2), the reaction temperature is 0-40 ℃.

9. The method for producing the dimethylochronoid rare earth complex according to claim 3, which comprises: the step (3) comprises the following more specific steps:

3-1) mixing a dimethobilin ligand and an alkali in a water-soluble organic solvent, and deprotonating the ligand;

3-2) mixing the reaction liquid obtained in the step 3-1) with rare earth metal salt to perform metal complex reaction to generate dimethylchbile-class rare earth complex;

preferably, in the step 3-1), the deprotonation temperature of the ligand is 0-60 ℃;

preferably, in the step 3-1), the molar ratio of the dimethobilin ligand to the alkali is 2-2.5: 3;

preferably, in the step 3-2), the temperature of the metal complexing reaction is 0-60 ℃;

preferably, in the step 3-2), the rare earth metal salt includes at least one of a chloride, a bromide, a nitrate, a perchlorate, a carboxylate, a fluoborate or a hexafluorophosphate of the rare earth metal;

preferably, the molar ratio of the rare earth metal to the dimethobilin ligand is 1: 2-2.5.

10. Use of the dimethylchthobilin rare earth complex according to claim 1 or 2 for the preparation of a display or a lighting device.

Technical Field

The invention relates to the technical field of rare earth materials, in particular to a dimethylchnane pigment rare earth complex and a preparation method and application thereof.

Background

The rare earth element is a general name of 17 elements including lanthanide elements, scandium and yttrium in the periodic table of elements, and has wide application in the fields of catalysis, high-performance magnets, metallurgy, batteries, ceramics, agriculture and the like. The rare earth complex has luminescence property derived from lanthanide series metal trivalent ion (Ln)³⁺) F-f transition of (c). This transition belongs to the internal energy of the atomThe transition of the levels, and therefore the emission lines, is nearly linear with a full width at half maximum (FWHM) typically less than 10nm, and this monochromaticity is almost impossible to achieve with luminescent materials made with molecular fluorescence, phosphorescence or Thermally Activated Delayed Fluorescence (TADF). At the same time due to 5s²And 5p⁶The shielding effect of electrons, the 4f electron layer is hardly influenced by the external coordination environment, and the result is that the characteristic spectral line emitted by lanthanide ions is not changed by modifying the ligand. Therefore, the lanthanide series luminescent material has important application value in the display field.

The wavelength coverage of the rare earth complex luminescence is wide: from UV (Gd)³⁺) To visible light (Sm)³⁺、Eu³⁺、Tb³⁺、Dy³⁺、Tm³⁺) To near infrared (Nd)³⁺、Er³⁺、Yb³⁺) Wherein Eu is³⁺And Tb³⁺Has received attention because of its strong emission peak in the visible region. Eu (Eu)³⁺The main emission peak of the fluorescent material is 613nm and is red light; tb³⁺Has a main emission peak around 545nm, and is green light. The red light and the green light are basic components constituting the RGB three primary color light display mode, and the importance of the corresponding light emitting materials in the display field is self-evident.

The luminescence of the rare earth metal ions is generated by f-f transition, but because the luminescence is a spin forbidden process in quantum mechanics, the rare earth metal ions often need to realize a high-efficiency photosensitive emission process by means of the sensitization of ligands. Since the first realization of devices using terbium acetylacetonate complexes as the luminescent material by the Kido group in 1990, a large number of rare earth luminescent materials and devices have been reported, and the maximum luminous efficiency of the laboratory has exceeded 80%. However, the lifetime and the practical efficiency of these light-emitting devices have not yet reached theoretical values, mainly due to the poor photostability of the rare earth complexes.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a dimethylochroletin rare earth complex Na [ LnL₂]The dimethylcholines rare earth complex has good luminescence stability.

The invention also provides a preparation method and application of the dimethylcrochromycin rare earth complex.

Specifically, the invention adopts the following technical scheme:

the first aspect of the invention provides a dimethylchnane-type rare earth complex, which has a structural formula shown in formula 1 as follows:

wherein R is an electron-withdrawing group, and Ln is a lanthanide.

Preferably, the R is a strong electron-withdrawing group and comprises at least one of trifluoromethyl, pentafluorophenyl, nitro and trihalomethyl.

The second aspect of the invention provides a preparation method of a dimethylchtanshin-type rare earth complex, which comprises the following steps:

(1) dipyrromethene compoundsNucleophilic substitution reaction is carried out to prepare diacyl-substituted dipyrromethane compound

(2) Diacyl-substituted dipyrromethenesReacting with pyrrole to obtain dimethylochrolenin ligand

(3) Reacting a rare earth metal salt with a dimethobilin ligandReaction to form IIMethanechol rare earth complex

Wherein R is an electron-withdrawing group, and Ln is a lanthanide.

The preparation process has the following route:

preferably, the R is a strong electron withdrawing group including trifluoromethyl, pentafluorophenyl, nitro, trihalomethyl and the like.

The step (1) is specifically that the dipyrromethane compound is mixed with a Grignard reagent for Grignard reaction, and then the acyl halide compound is addedCarrying out nucleophilic substitution reaction to generate diacyl-substituted dipyrromethane compound; the X represents halogen.

Step (1) is carried out under anhydrous conditions, and the reaction can be carried out in an anhydrous solvent (such as anhydrous toluene) and dry air (or inert gas) during specific operation.

In the step (1), the temperature of the Grignard reaction and the nucleophilic substitution reaction is independently 0-40 ℃, and is preferably performed at room temperature.

In the step (1), the Grignard reaction time is 20-40 minutes; the time of the nucleophilic substitution reaction is 20-40 minutes.

In the step (1), the molar ratio of the Grignard reagent to the dipyrromethane compound is greater than 2: 1.

In the step (1), the acyl halide compound is preferably an acyl chloride compound, and comprises at least one of trifluoroformyl chloride and pentafluorobenzoyl chloride. The molar ratio of the acyl chloride compound to the dipyrromethane compound is greater than 2: 1.

In the step (1), after the nucleophilic substitution reaction is finished, a separation and purification step is further included. The separation and purification steps are specifically as follows: standing and layering the reaction mixed solution, extracting the water layer after standing by adopting an organic solvent, and then washing and drying the extracted organic phase to obtain a concentrated solution; and carrying out column chromatography separation on the concentrated solution to obtain the diacyl-substituted dipyrromethane compound. Wherein the organic solvent used for extraction is ester solvent such as ethyl acetate; the eluent in the column chromatography separation adopts an ethyl acetate-petroleum ether mixed solution, and the volume ratio of ethyl acetate to petroleum ether is 1: 4-6, preferably 1: 5.

In the step (1), the dipyrromethane compound is obtained by electrophilic substitution reaction of pyrrole and benzophenone. Specifically, pyrrole and benzophenone are mixed, and electrophilic substitution reaction is carried out under the action of a catalyst, so as to obtain the dipyrromethane compound. The catalyst is Lewis acid, and the Lewis acid comprises at least one of boron trifluoride, boron trifluoride-diethyl ether and titanium tetrachloride. The molar ratio of pyrrole to benzophenone is greater than 2: 1. The temperature of the nucleophilic substitution reaction is 0-40 ℃, and room temperature is preferred.

The step (2) comprises the following more specific steps:

2-1) firstly, carrying out reduction reaction on a reducing agent and a diacyl-substituted dipyrromethane compound, and reducing carbonyl in the diacyl-substituted dipyrromethane compound into hydroxyl to obtain an intermediate 1;

2-2) then mixing the intermediate 1 with pyrrole, a catalyst, an oxidant and alkali, and reacting to generate the dimethylcholines ligand.

In the step 2-1), the temperature of the reduction reaction is 0-40 ℃, and the reduction reaction is preferably carried out at room temperature; the time of the reduction reaction is 1 to 3 hours, preferably about 2 hours.

In the step 2-1), the reducing agent comprises at least one of sodium borohydride, lithium aluminum hydride and diisobutyl aluminum hydride, and the molar ratio of the reducing agent to the diacyl-substituted dipyrromethane compound is 50-55: 1.

In the step 2-1), the reduction reaction is carried out in a methanol-tetrahydrofuran mixed solvent, wherein the volume ratio of methanol to tetrahydrofuran is 1: 2-4, and 1:3 is preferred.

In the step 2-1), after the reduction reaction is finished, the method further comprises the step of separating and purifying the intermediate 1. The separation and purification steps are specifically as follows: and extracting the reaction solution by using an organic solvent, and then washing, drying and concentrating an extracted organic phase to obtain a concentrated solution. Among them, the organic solvent used for extraction may be a medium or high polar solvent such as dichloromethane, chloroform, diethyl ether, etc.

In the step 2-2), the reaction temperature is 0-40 ℃, and preferably the reaction is carried out at room temperature; the reaction time is 1 to 3 hours, preferably about 2 hours.

In the step 2-2), the oxidizing agent comprises dichloro dicyano benzoquinone. The catalyst comprises at least one of indium trichloride, indium tribromide and indium triiodide, and the indium trichloride, the indium tribromide and the indium triiodide belong to Lewis acid. The base comprises at least one of triethylamine, diisopropylethylamine, pyridine, and thiomorpholine for accepting protons.

In the step 2-2), after the reaction is finished, a separation and purification step is further included. The separation and purification steps are specifically as follows: removing solvent, and separating by column chromatography to obtain dimethylochrolenin ligand. The eluent in the column chromatography separation adopts a petroleum ether-dichloromethane mixed solution, and the volume ratio of the petroleum ether to the dichloromethane is 1.5-2.5: 1, preferably 2: 1.

The step (3) comprises the following more specific steps:

3-1) mixing a dimethobilin ligand and an alkali in a water-soluble organic solvent, and deprotonating the ligand;

3-2) mixing the reaction liquid obtained in the step 3-1) with rare earth metal salt to carry out metal complex reaction to generate dimethylchbile-class rare earth complex.

In the step 3-1), the deprotonation temperature of the ligand is 0-60 ℃, and the time is 10-20 minutes.

In the step 3-1), the water-soluble organic solvent comprises at least one of acetonitrile, methanol and toluene; the alkali comprises at least one of sodium hydroxide, potassium hydroxide and potassium carbonate; the molar ratio of the dimethobilin ligand to the alkali is 2-2.5: 3.

In the step 3-2), the temperature of the metal complexing reaction is 0-60 ℃, and the time is 20-30 hours.

In the step 3-2), the rare earth metal salt comprises at least one of lanthanide metal chloride, bromide, nitrate, perchlorate, carboxylate, fluoborate or hexafluorophosphate; the lanthanide metal includes at least one of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

The molar ratio of the rare earth metal to the dimethobilin ligand is 1: 2-2.5.

In the step 3-2), after the metal complexing reaction is finished, filtering, washing and drying the mixture while the mixture is hot to obtain the dimethylchcholines rare earth complex.

The third aspect of the invention is to provide the application of the dimethylchroletin rare earth complex in preparing a display or a lighting device.

The invention has the following beneficial effects:

compared with rare earth complexes prepared from porphyrin and other common tetrapyrrole ligands, the dimethylchrolene rare earth complex has no aromaticity, so that the triplet state energy level is higher than that of porphyrin, the problem that the triplet state energy of porphyrin is not enough to sensitize rare earth ions, particularly europium and terbium ions, can be effectively solved, and the stability of the complex combined by the porphyrin tetradentate ligand is maintained.

The dimethylchcholerycin rare earth complex can emit yellow light and red light; and the luminous intensity is low after long-time luminescence, and the fluorescent material has good luminous stability and good application prospect in the fields of display and illumination. The preparation method has the advantages of few steps and high product purity, and greatly reduces the production cost of the product.

Detailed Description

The technical solution of the present invention is further described below with reference to specific examples. In the following description, unless otherwise specified, the ice bath corresponds to a temperature of about 0 ℃ and a room temperature of 15 to 25 ℃.

Synthesis of sodium bis (10, 10-diphenyl-5, 15-dipentafluorophenyldimethylbile pigment) europium oxide:

the first step is as follows: preparation of 5, 5-diphenyl dipyrromethane

Benzophenone 10.04g (55mmol) was charged into a 250mL reaction flask, followed by addition of degassed ethanol (100mL), pyrrole (10mL) and boron trifluoride etherate (10mL) to the flask, respectively, under a nitrogen blanket. The reaction mixture was stirred at room temperature for 5 days to give a large amount of white solid and a dark red solution. Filtration gave the crude product, which was dried under vacuum to give 6.8g of Compound 1(5, 5-diphenyldipyrromethane) as a white powder.

Process for preparation of Compound 1¹H NMR(600MHz,DMSO)δ/ppm:10.28(s,2H),7.32-7.17(m,6H),6.94-6.87(m,4H),6.71(s,2H),5.91(s,2H),5.56(s,2H)。

The second step is that: 5, 5-diphenyl-1, 9-dipentafluorophenylacyldipyrromethane

1.5g of Compound 1 are dissolved in 100mL of anhydrous toluene under nitrogen protection, and to the resulting solution ethyl magnesium bromide (25mL of a 1M solution in THF) is slowly added dropwise. After stirring the reaction for half an hour, pentafluorobenzoyl chloride (1.8mL, diluted with 10mL of anhydrous toluene and added) was added dropwise slowly to the solution, and after stirring for half an hour, 80mL of saturated ammonium chloride solution was added to terminate the reaction. The mixed solution is kept stand for layering, the water phase is extracted for a plurality of times by ethyl acetate, the organic phase is combined and washed by distilled water and saturated sodium chloride solution (150 mL respectively), and then anhydrous sodium sulfate is added for drying. The dried solution was concentrated and then separated by column chromatography (eluent was a mixture of ethyl acetate and petroleum ether at a volume ratio of 1: 5) to give compound 2(5, 5-diphenyl-1, 9-dipentafluorophenylacyldipyrromethane), and compound 2 was recrystallized from dichloromethane and petroleum ether to give 2.9g of a white solid.

Process for preparation of Compound 2¹H NMR(600MHz,CDCl₃)δ/ppm:9.13(s,2H),7.40(m,6H),7.10(m,4H),6.71(s,2H),6.22(dd,J＝4.1,2.7Hz,2H)；¹³C NMR(150MHz,CDCl₃)δ/ppm:172.2,144.8,144.4,143.1,142.0,138.5,136.8,131.1,129.1,129.0,128.4,121.2,113.8；¹⁹F NMR(565MHz,CDCl₃,25℃)δ/ppm:-139.78(dd,J＝23.6,8.3Hz,4F),-150.65(t,J＝20.7Hz,2F),-159.96(td,J＝29.8,16.4Hz,4F)。

The third step: preparation of 10, 10-diphenyl-5, 15-dipentafluorophenyldimethylcholine pigment

343mg of compound 2 was dissolved in 40mL of a 3:1 tetrahydrofuran-methanol mixed solution, and 946mg of sodium borohydride was added thereto under cooling in an ice bath. After 10 minutes, the mixture was stirred at room temperature for another 2 hours, and then a saturated ammonium chloride solution was added to terminate the reaction. Extracting the obtained reaction liquid with dichloromethane for several times, combining organic phases, washing with distilled water and saturated sodium chloride solution in sequence, and finally adding anhydrous sodium sulfate to dry.

After drying, the solution was concentrated and the residue redissolved in 200mL of dichloromethane, followed by addition of a minor amount of indium trichloride (15mg) and pyrrole (100L), and stirred for 30min to give a pale pink solution. DDQ (2, 3-dichloro-5, 6-dicyan-p-benzoquinone, 180mg) was then added, stirred for 5 minutes and then supplemented with 14mL triethylamine. The mixed system was reacted for 2 hours, and then the solvent was removed to obtain a crude product, which was separated by column chromatography (petroleum ether: dichloromethane 2:1 as eluent) to obtain 283mg of an orange solid, i.e., compound 3(10, 10-diphenyl-5, 15-dipentafluorophenyldimethylsichuan bile pigment).

Process for preparation of Compound 3¹H NMR(600MHz,DMSO)δ/ppm:11.82(s,2H),7.46-7.43(m,4H),7.40-7.38(m,2H),7.21(d,J＝6Hz,4H),7.17(s,2H),7.04(d,J＝6.0Hz,2H),6.55(d,J＝6.0Hz,4H),6.25-6.23(m,2H)；¹³C NMR(150MHz,DMSO)δ/ppm:175.3,147.2,145.3,144.0,143.1,140.9,138.0,137.0,132.7,131.5,131.4,130.1,128.6,128.4,127.8,122.8,121.8,113.2,110.9,62.2.¹⁹F NMR(376MHz,DMSO)δ/ppm-140.84(dd,J＝25.2,7.2Hz),-154.34(t,J＝22.5Hz),-161.93(td,J＝24.3,7.4Hz)。

The fourth step: preparation of sodium bis (10, 10-diphenyl-5, 15-dipentafluorophenyldimethylbile pigment) europium oxide

1g of Compound 3 was dissolved in 100mL of acetonitrile to prepare a solution, and about 50mL of an aqueous sodium hydroxide solution (prepared by dissolving 100mg of sodium hydroxide in 10mL of water) was added dropwise to the solution, and after the obtained solution was stirred and reacted for 15 minutes, 50mL of an aqueous europium trichloride solution (prepared by dissolving 230mg of europium trichloride hexahydrate in 50mL of distilled water) was added dropwise. After the dropwise addition, the mixture is heated and stirred for 24 hours at 60 ℃, and after the reaction is finished, the mixture is filtered while the mixture is hot. The filter residue was washed with ethanol/water solution and then vacuum-dried for 2 hours to obtain 830mg of a pale yellow solid, i.e., compound 4[ bis (10, 10-diphenyl-5, 15-dipentafluorophenyldimethylsichuan bile pigment) europium sodium salt ].

ESI-MS:m/z＝1741[M+H]⁺。

As can be known from fluorescence emission spectrum tests, the fluorescence emission wavelength of the compound 4 is 594nm and 618nm, which are characteristic emission wavelengths of europium ions, and yellow light and red light can be emitted; and the emission intensity of the compound 4 is reduced to about 80 percent after being irradiated by UV of 365nm for 168 hours, and the complex Na [ Eu (tta) ] prepared by beta-diketone ligand under the same condition₄]The emission intensity (formula 2) rapidly decreased to less than the first 10% within 20 hours, reflecting the excellent photostability of compound 4. . According to the property of the compound 4, the compound 4 and similar dimethylchbilin rare earth complexes can be applied to the preparation of displays, lighting devices and the like.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.