CN112812049B - Dimethylcholines rare earth complex and preparation method and application thereof - Google Patents

Dimethylcholines rare earth complex and preparation method and application thereof Download PDF

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CN112812049B
CN112812049B CN202011633082.5A CN202011633082A CN112812049B CN 112812049 B CN112812049 B CN 112812049B CN 202011633082 A CN202011633082 A CN 202011633082A CN 112812049 B CN112812049 B CN 112812049B
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宋森川
史华红
麦裕良
文武
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract

The invention discloses a dimethylchnane pigment rare earth complex and a preparation method and application thereof, wherein the dimethylchnane pigment rare earth complex is prepared by using dimethylchnane pigmentThe structural formula of the element rare earth complex is

Description

Dimethylchcholeryn rare earth complex and preparation method and application thereof
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 transition of the internal energy levels of the atoms and therefore has a nearly linear emission line with a full width at half maximum (FWHM) of typically less than 10nm, which 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 5s 2 And 5p 6 Due to the shielding effect of electrons, the 4f electron layer is hardly influenced by the external coordination environment, and the characteristic spectral line emitted by lanthanide ions cannot be changed due to the modification of ligands. 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+ 、Eu 3+ 、Tb 3+ 、Dy 3+ 、Tm 3+ ) To near infrared (Nd) 3+ 、Er 3+ 、Yb 3+ ) Wherein Eu is 3+ And Tb 3+ Has attracted 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; tb 3+ Has a main emission peak around 545nm, and is green light. Red and green light compositionThe basic components of the RGB light display mode, and the importance of the corresponding light emitting material in the display field, are 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 an efficient 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 [ LnL 2 ]The dimethylcholines rare earth complex has good luminescence stability.
The invention also provides a preparation method and application of the dimethylchcholerycin 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:
Figure BDA0002877450750000021
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) reacting dipyrroleMethane compound
Figure BDA0002877450750000022
Nucleophilic substitution reaction is carried out to prepare diacyl-substituted dipyrromethane compound
Figure BDA0002877450750000023
(2) Diacyl-substituted dipyrromethenes
Figure BDA0002877450750000024
Reacting with pyrrole to obtain dimethylochrolenin ligand
Figure BDA0002877450750000031
(3) Reacting a rare earth metal salt with a dimethobilin ligand
Figure BDA0002877450750000032
Reaction to generate dimethylchbile-class rare-earth complex
Figure BDA0002877450750000033
Wherein R is an electron-withdrawing group, and Ln is a lanthanide.
The preparation process has the following route:
Figure BDA0002877450750000034
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 added
Figure BDA0002877450750000041
Nucleophilic substitution reaction is carried out to generate diacyl-substituted dipyrromethane compound(ii) a 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 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 dimethochnol ligands 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 dimethylchcholeryanine rare earth complex in the preparation of displays or lighting devices.
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
Figure BDA0002877450750000061
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 1 1 H 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
Figure BDA0002877450750000071
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 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 2 1 H NMR(600MHz,CDCl 3 )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)； 13 C NMR(150MHz,CDCl 3 )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； 19 F NMR(565MHz,CDCl 3 ,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
Figure BDA0002877450750000081
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-dipentafluorophenyldimethylbile pigment).
Process for preparation of Compound 3 1 H 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)； 13 C 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. 19 F 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
Figure BDA0002877450750000091
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 condition 4 ]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.
Figure BDA0002877450750000092
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.

Claims (15)

1. A dimethylchnane pigment rare earth complex is characterized in that: the dimethylcholines rare earth complex has a structural formula shown in formula 1:
Figure 749824DEST_PATH_IMAGE001
formula 1
Wherein R is pentafluorophenyl, nitro or trihalomethyl, and Ln is a lanthanide.
2. A method for preparing dimethylchtanshin-class rare earth complex is characterized by comprising the following steps: the method comprises the following steps:
(1) reacting dipyrromethane compounds
Figure 572286DEST_PATH_IMAGE002
Nucleophilic substitution reaction is carried out to prepare diacyl-substituted dipyrromethane compound
Figure 777003DEST_PATH_IMAGE003
；
(2) Diacyl-substituted dipyrromethenes
Figure 975903DEST_PATH_IMAGE004
Reacting with pyrrole to obtain dimethylochrolenin ligand
Figure 644782DEST_PATH_IMAGE005
；
(3) Reacting a rare earth metal salt with a dimethobilin ligand
Figure 575829DEST_PATH_IMAGE006
Reaction to generate dimethylchbile-class rare-earth complex
Figure 330158DEST_PATH_IMAGE007
；
Wherein R is pentafluorophenyl, nitro or trihalomethyl, and Ln is a lanthanide.
3. The method for producing the dimethylochronoid rare earth complex according to claim 2, 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 added
Figure 67170DEST_PATH_IMAGE008
Nucleophilic substitution reaction is carried out to generate diacyl substituted dipyrromethane compounds; the X tableRepresents halogen.
4. The method for producing the dimethylochronoid rare earth complex according to claim 3, which comprises: the step (1) is carried out under anhydrous conditions.
5. The method for producing the dimethylochronoid rare earth complex according to claim 3, which comprises: in the step (1), the temperature of the Grignard reaction and the nucleophilic substitution reaction is independently 0-40 ℃.
6. The method for producing the dimethylochronoid rare earth complex according to claim 2, 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.
7. The method for producing a dimethylchnahostatin-based rare earth complex according to claim 6, wherein: in the step 2-1), the temperature of the reduction reaction is 0-40 ℃.
8. The method for producing the dimethylochronoid rare earth complex according to claim 6, which comprises: in the step 2-1), the molar ratio of the reducing agent to the diacyl-substituted dipyrromethane compound is 50-55: 1.
9. The method for producing the dimethylochronoid rare earth complex according to claim 6, which comprises: in the step 2-2), the reaction temperature is 0-40 ℃.
10. The method for producing the dimethylochronoid rare earth complex according to claim 2, 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 carry out metal complex reaction to generate dimethylchbile-class rare earth complex.
11. The method for producing the dimethylochronoid rare earth complex according to claim 10, which comprises: in the step 3-1), the deprotonation temperature of the ligand is 0-60 ℃.
12. The method for producing the dimethylochronoid rare earth complex according to claim 10, which comprises: in the step 3-1), the molar ratio of the dimethobilin ligand to the alkali is 2-2.5: 3.
13. The method for producing the dimethylochronoid rare earth complex according to claim 10, which comprises: in the step 3-2), the temperature of the metal complexing reaction is 0-60 ℃.
14. The method for producing the dimethylochronoid rare earth complex according to claim 10, which comprises: in the step 3-2), the rare earth metal salt comprises at least one of chloride, bromide, nitrate, perchlorate, carboxylate, fluoborate or hexafluorophosphate of the rare earth metal;
the molar ratio of the rare earth metal to the dimethochnane ligand is 1: 2-2.5.
15. The use of the dimethylchcholeryanine rare earth complex of claim 1 in the preparation of displays or lighting devices.
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