CN113527211A - Styryl-containing phenanthroimidazole luminescent material and preparation method and application thereof - Google Patents
Styryl-containing phenanthroimidazole luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a styryl-containing phenanthroimidazole luminescent material and a preparation method and application thereof. Carbonyl-containing compounds and (4-cyanobenzyl) diethyl phosphonate are used as raw materials, and the styryl-containing phenanthroimidazole compound is prepared through a Wittig-Honor reaction, a reduction reaction and a debus-radziszewski 'one-pot method'. The method can utilize the characteristic infrared absorption of formyl and cyano in infrared spectrum to monitor the reaction process; the carbon-carbon coupling reaction catalyzed by noble metal is avoided in the reaction process; and the yield is high. Provides a new method for synthesizing the styryl-containing phenanthroimidazole compound. In addition, the styryl-containing phenanthroimidazole compound provided by the invention can be used as an organic luminescent material and directly applied to an ultraviolet-excited organic/inorganic hybrid white light LED device, and provides technical reference for the application of the organic/inorganic hybrid white light LED device.
Description
Technical Field
The invention belongs to the field of organic chemistry and photoelectric materials, and particularly relates to a styryl-containing phenanthroimidazole luminescent material as well as a preparation method and application thereof.
Background
The organic luminescent material is used as a blue light/ultraviolet LED down-conversion material to prepare an inorganic/organic hybrid white light LED device, and compared with a full-inorganic LED device, the device can reduce the dependence on rare earth metal materials to a certain extent, thereby bringing about wide attention of technicians in the field.
Organic blue-green materials are a class of materials that emit both blue and green light. The organic blue-green light material is applied to an organic/inorganic hybrid white light LED device, so that the color rendering index of the device can be improved. The phenanthroimidazole derivative becomes a luminescent material with very high use frequency by virtue of simple synthesis, low cost, high yield and high quantum yield, and the compound can be prepared by a one-pot method. Through styryl bridging phenanthroimidazole and other luminescent groups (triphenylamine, carbazole and the like), prolonged molecular conjugation can be realized so as to construct a blue-green light material, but the construction of the styryl-containing phenanthroimidazole luminescent material is generally constructed by adopting a carbon-carbon coupling reaction in the literature, the use of a noble metal catalyst cannot be avoided in the reaction process, and the reaction process cannot be monitored by utilizing obvious characteristic functional groups (Journal of Physical Organic Chemistry, 2017, 30 (12) e 3695.). Therefore, the design and synthesis of the styryl-containing phenanthroimidazole luminescent material which is novel in structure, avoids the use of a noble metal catalyst in the synthesis process, is easy to monitor the reaction process, and can be applied to the excitation of an ultraviolet LED chip are extremely important.
Disclosure of Invention
One of the purposes of the invention is to provide novel styryl-containing phenanthroimidazole compounds which can be used as organic luminescent materials to be applied to ultraviolet LED chip excitation to construct organic/inorganic hybrid LED luminescent devices.
The second purpose of the invention is to provide a preparation method of phenanthroimidazole compounds for synthesizing styryl.
The invention also aims to provide application of the compound.
A kind of styryl-containing phenanthroimidazole luminescent material has the following chemical structure:
wherein R is1The group is triphenylamine or carbazole derivative;
R2the group is selected from one of hydrogen, methyl, methoxy, tertiary butyl, halogen and halogen substituted methyl.
In a further improvement, the triphenylamine or carbazole derivative is any one of structures shown in II:
the preparation method of the styryl-containing phenanthroimidazole luminescent material is characterized in that the styryl-containing phenanthroimidazole compound is prepared through a Wittig-Honor reaction, a reduction reaction and a debus-radziszewski 'one-pot method', and the process only needs to be carried out through three steps: the synthetic route is as follows:
the synthesis steps of the styryl-containing phenanthroimidazole luminescent material are as follows:
step one, substituent (R)1) Formaldehyde (carbonyl compound): diethyl (4-cyanobenzyl) phosphonate: potassium tert-butoxide in a molar ratio of 1-10.4: 1.2-11.6: dissolving the raw materials in a solvent according to a molar ratio of 1.5-10.4 for reaction, monitoring the reaction by a thin layer chromatography method, and purifying a reaction product by column chromatography to obtain a compound 1;
secondly, weighing the compound 1 under the inert gas atmosphere, placing the compound in a three-neck flask, and adding diisobutyl aluminum hydride solution into a reaction system at the temperature of between 77 ℃ below zero and 22 ℃ below zero; the molar ratio of the compound 1 to the diisobutylaluminum hydride is 1-2: 2.5-7.5; monitoring the completion of the reaction through thin layer chromatography, adding an HCl solution to adjust the pH value to 1-5, extracting with ethyl acetate, combining ethyl acetate, drying, and performing rotary evaporation to recover ethyl acetate to obtain a compound 2;
weighing a compound 2, phenanthrenequinone, aniline or aniline derivative, mixing ammonium acetate and acetic acid in a three-neck flask to form a reaction system, adopting inert gas for protection, heating to rise the temperature until the reaction system refluxes, monitoring the reaction endpoint through a thin-layer chromatography method, stopping heating, returning the temperature of the reaction system to room temperature, adding deionized water, pouring the solution into a separating funnel, adding an ethyl acetate extraction solution, repeatedly extracting a water phase until the water phase is clear, combining ethyl acetate extraction solutions, and then performing column chromatography chromatographic separation to obtain the styryl-containing phenanthroimidazole luminescent material; wherein the mol ratio of the compound 2, the phenanthrenequinone, the aniline or aniline derivative and the ammonium acetate is 1: 1-1.2: 1: 16.
further improvement: the thin layer chromatography method realizes the monitoring of the reaction process through the disappearance and the reappearance of characteristic absorption peaks of carbonyl and cyano in the infrared spectrum.
The application of the styryl-containing phenanthroimidazole luminescent material is characterized in that the styryl-containing phenanthroimidazole luminescent material is used in an organic/inorganic hybrid LED device excited by ultraviolet light energy.
In a further improvement, the wavelength of the ultraviolet light is 300-400 nm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention synthesizes a styryl-containing phenanthroimidazole compound, the synthesis method of the compound is simple, a target product can be obtained through three steps of reactions, and the synthesis route involves the conversion of compounds containing formyl radicals: in the first step, the raw material formyl compound is converted into an intermediate containing cyano; in the second step, the intermediate containing cyanogen is converted into the intermediate containing formyl; and thirdly, converting the intermediate containing the formyl group into an imidazole group to realize the conversion of the target product, namely the styryl-containing phenanthroimidazole compound. In the above reaction steps, there are two important features: 1) the characteristic infrared absorption of formyl and cyano in the infrared spectrum can be utilized to monitor the reaction process; 2) no noble metal catalyst is used in the reaction process. Compared with the prior art, the method has the advantages that the reaction is easy to monitor, and the carbon-carbon coupling reaction catalyzed by noble metal is not used, so that the method has good practical significance. In addition, the styryl-containing phenanthroimidazole compound provided by the invention can be used as an organic luminescent material and directly applied to an ultraviolet-excited organic/inorganic hybrid white light LED device.
Drawings
FIG. 1 is an infrared spectrum of an intermediate and a product prepared according to the first embodiment of the present invention.
FIG. 2 is a drawing of a copolymer prepared in accordance with one embodiment of the present inventionEA structural schematic diagram, a nuclear magnetic hydrogen spectrum (a) and a nuclear magnetic carbon spectrum (b) of the compound of (E) -1- (4 '-triphenylamine) -2- (4', 1 '' -phenyl-4 '' -phenyl-phenanthroimidazole) -ethylene.
FIG. 3 is a drawing of a sample of the invention prepared in accordance with example oneE-1- (4 '-triphenylamino) -2- (4', 1 "-phenyl-4" -phenyl-phenanthroimidazole) -ethylene mass spectrum.
FIG. 4 is a schematic diagram of an embodiment of the present inventionEPreparation of (E) -1- (4 '-triphenylamine) -2- (4', 1 '' -phenyl-4 '' -phenyl-phenanthroimidazole) -ethylene to obtain a spectrum (a) and a color coordinate (b) diagram of an organic/inorganic hybrid LED device.
Detailed Description
For a better understanding of the present invention, the following detailed description will now be given, and examples will be given to further explain and illustrate the present invention, but the present invention is not limited to the following examples.
(1) A substituent (R)1) Formaldehyde: diethyl (4-cyanobenzyl) phosphonate: the proportion of potassium tert-butoxide is 1-4: 1.2-4.8: 1.5-3, adding the raw materials into a certain amount of solvent, and detecting the completion of the reaction by a thin layer chromatography method. By column chromatography pairThe crude product is purified to obtain a liquid or solid product, and the maximum yield can reach 97%.
(2) Weighing the light yellow solid synthesized in the step (1) under the inert gas atmosphere condition, placing the light yellow solid in a three-neck flask, and adding a diisobutylaluminum hydride (reducing agent) toluene solution with the concentration of 1 mol/L-2.5 mol/L and the material ratio of 1: 1-1: 12 into a reaction system at-77 to-22 ℃. The end of the reaction was monitored by thin layer chromatography. Adding 10-30% HCl to adjust the pH value to 1-5. Then, ethyl acetate is adopted for extraction, organic phases are combined, the solvent is dried and then is subjected to rotary evaporation to recover the solvent, a liquid or solid sample can be obtained, and the maximum yield can reach 82%.
(3) Weighing the product obtained in the step (2), 9, 10-phenanthrenequinone and R2Substituted aniline, ammonium acetate and acetic acid are mixed in a three-neck flask. Then argon is adopted to protect the reaction system, heating is started, and the temperature is slowly raised until the reaction system refluxes. The end of the reaction was monitored by thin layer chromatography. Stopping heating, returning the temperature of the system to room temperature, adding deionized water, pouring the solution into a separating funnel, adding a proper amount of ethyl acetate extraction solution, and repeatedly extracting the water phase until the water phase is clear. The final product can be obtained by column chromatography and chromatographic separation after the organic phases are combined, and the maximum yield can reach 88%.
(4) And (2) taking the styryl-containing phenanthroimidazole compound in the step (3) as an organic luminescent material, uniformly mixing the styryl-containing phenanthroimidazole compound in silica gel according to a certain proportion (wherein the silica gel consists of a main gel A and a curing agent B, the proportion of A to B is 1: 4), coating the mixture on an ultraviolet LED chip (the specification is 0.1-3W, and the main wavelength range is 300-400 nm), and curing to obtain the organic/inorganic hybrid LED device. The luminous efficiency of the device can reach 10-20 lm/W.
Example 1:
preparation of E-1- (4 '-triphenylamino) -2- (4', 1 '-phenyl-4' -phenyl-phenanthroimidazole) -ethene
(1) 0.274g (1mmol) of 4-formyltriphenylamine, 0.1683g (1.5mmol) of potassium tert-butoxide,10mL of DMF (dimethylformamide) (1 mL (1.2 mmol)) and 1mL (4-cyanobenzyl) diethyl phosphonate are put in a 50mL three-necked flask, deionized water is added after the reaction is tracked to the end point by adopting thin layer chromatography, ethyl acetate is adopted for extraction for 3 times, organic phases are combined and dried for 24 hours by using anhydrous magnesium sulfate, and after filtration and column chromatography separation, 0.34g of yellow powder (the compound 1 in the reaction route) is obtained, and the yield is 93%.1H NMR(300MHz,CDCl3) δ 7.57(dd, J ═ 20.4,8.1Hz,2H),7.39(d, J ═ 8.5Hz, 2H), 7.35-7.17 (m,6H), 7.16-7.02 (m,8H),6.95(d, J ═ 16.3Hz, 2H). The infrared spectrum is shown in FIG. 1(1-CN), and the characteristic absorption position in the spectrum is 2225cm-1Here, it is the characteristic absorption peak of a cyano group.
(2) 10.3412 g (1mmol) of compound and 5 mL of toluene are weighed into a 50mL round-bottom flask, 1mL of diisobutylaluminum hydride 2.5 mol/L is added under argon atmosphere at-44 ℃ to react for 4 hours, the reaction is stopped, the pH is adjusted to 4 by 10% hydrochloric acid, and the mixture is filtered and dried to obtain 0.26 g of yellow solid (compound 2 in the reaction scheme), wherein the yield is 76%.1H NMR (300 MHz, CDCl3) δ 9.98 (s, 1H), 7.85 (d, J = 8.2 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.41 (d, J= 8.6 Hz,2H), 7.33-7.17 (m,6H), 7.16-6.95 (m, 8H). The infrared spectrum is shown in FIG. 1 (2-CHO), and the characteristic absorption position in the spectrum is 1700 cm-1 cm-1Here, the characteristic absorption of carbonyl group.
(3) Weighing compound 2 (0.37 g and 1mmol), 0.1118 g aniline (1.2mmol), 0.2082 g phenanthrenequinone (1mmol), 1.322 g ammonium acetate (16 mmol) and 40mL acetic acid in a 100mL round-bottom flask, performing reflux reaction for 48 h, adding deionized water, extracting for 3 times by ethyl acetate, combining organic phases, drying over anhydrous magnesium sulfate for 24 h, filtering, and separating by column chromatography to obtain 0.3055 g, wherein the yield is 83%.1H NMR (300 MHz, CDCl3) δ 9.01 (d, J= 9.0 Hz, 1H), 8.74 (dd, J = 19.4, 8.3 Hz, 2H), 7.75 (dd, J = 18.0, 10.2 Hz, 2H), 7.69 – 7.46 (m, 10H), 7.46 – 7.29 (m, 7H), 7.21 – 6.99 (m, 10H), 6.92 (d, J = 16.3 Hz, 1H)。13C NMR (101 MHz, CDCl3) δ 150.68, 147.60, 147.49, 138.91, 138.01, 137.55, 131.14, 130.23, 129.84, 129.54, 129.33, 129.28, 129.18, 129.13, 128.29, 128.25, 127.46, 127.30, 127.23, 126.28, 126.15, 126.07, 125.62, 124.87, 124.62, 124.13, 123.37, 123.17, 123.13, 123.06, 122.80, 120.87. The infrared spectrum is shown in figure 1 (target compound), and the characteristic absorption peak of carbonyl in the spectrum disappears, which indicates that the conversion of the compound 2 is completed. The hydrogen spectrum and carbon spectrum of the resulting target compound are shown in FIG. 2. The mass spectrum is shown in FIG. 3, indicating that the structure is correct.
In the embodiment, the raw materials of 4-formyl triphenylamine, potassium tert-butoxide, diisobutylaluminum hydride, aniline, phenanthrenequinone and the like can be commercially available products or products prepared by the disclosed method, reaction solvents are commercially available analytically pure, and the used deionized water is laboratory self-prepared water.
The synthesis method of the embodiment has the advantages of simple operation, low price and easy obtainment of raw materials, simple post-treatment, and easy infrared detection around the transformation of characteristic functional groups, namely formyl and cyano in a reaction route.
The synthetic route of this embodiment is as follows:
example 2:
preparation of E-1- (4 '-phenyl-carbazolyl) -2- (4', 1 '-phenyl-4' -phenyl-phenanthroimidazole) -ethylene
(1) Weighing 1.0851g (4mmol) of 4- (9H-carbazole) benzaldehyde, 0.1683g (1.5mmol) of potassium tert-butoxide, 40mL of dichloromethane (4.8mmol) and 4mL (4.8mmol) of diethyl (4-cyanobenzyl) phosphonate in a 100mL three-necked flask, tracking the reaction by thin layer chromatography, adding deionized water after the end point, extracting for 3 times by ethyl acetate, combining organic phases, drying for 24 hours by anhydrous magnesium sulfate, filtering, and separating by column chromatography to obtain a light yellow solid0.8728g (2.3mmol), 58% yield. External main absorption wave number of 3000cm-1、2225cm-1、1450cm-1、1250cm-1、550cm-1。1H NMR(300MHz, CDCl3)δ8.15(d,J＝7.3Hz,2H),7.83–7.50(m,8H),7.43(d,J＝5.3Hz,4H),7.36–7.08(m, 4H)。
(2) 0.8 g (2 mmol) of the pale yellow solid compound in the step (1) and 30 mL of toluene are weighed in a 100mL round-bottom flask, 3mL of diisobutylaluminum hydride 2.5 mol/L is added under argon atmosphere at-77 ℃ of a reaction system temperature, the reaction is stopped after 8 hours, the pH is adjusted to 1 by 30% hydrochloric acid, and 0.6356 g of yellow solid is obtained after filtration and drying, wherein the yield is 80%. Infrared main absorption wave number 1700 cm-1、1450cm-1、1200 cm-1、750 cm-1。1H NMR (300 MHz, CDCl3) δ 10.00 (s, 1H), 8.15 (d, J = 7.7 Hz, 2H), 7.89 (d, J = 8.1 Hz, 2H), 7.72 (dd, J = 19.6, 8.2 Hz, 4H), 7.59 (d, J = 8.3 Hz, 2H), 7.53 – 7.12 (m, 8H)。
(3) 0.3777 g (1mmol) of the yellow solid in (2), 0.2124 g (1mmol) of 9, 10-phenanthrenequinone and ammonium acetate were weighed under argon, and 7.5 mL of acetic acid was weighed and mixed in a 25 mL three-necked flask. The reaction was then blanketed with argon. And after reflux reaction for 72 h, adding deionized water after the temperature of the system is recovered to room temperature. The solution was poured into a separatory funnel and an appropriate amount of ethyl acetate extraction solution was added and the aqueous phase was extracted repeatedly until the aqueous phase was clear. The organic phases were combined and recovered by rotary evaporation to give an oil. Solidification with absolute ethanol gave a yellow solid, 0.6 g of yellow powder, a yield of 82%.1H NMR (400 MHz, CDCl3) δ 8.93 (d, J = 7.6 Hz, 1H), 8.81 (d, J = 8.4 Hz, 1H), 8.75 (d, J = 8.3 Hz, 1H), 8.18 (d, J= 7.7 Hz,2H), 7.84-7.41 (m, 19H), 7.37-7.13 (m, 7H). The infrared main absorption wave number is 3000cm-1、1700 cm-1、1500 cm-1、1450 cm-1、750 cm-1。
Example 3:
(1) 0.274g (1mmol) of 4-formyltriphenylamine, 0.1683g (3mmol) of potassium tert-butoxide, 20mL of dimethyl sulfoxide and 3mL (3.6mmol) of diethyl (4-cyanobenzyl) phosphonate are weighed in a 50mL three-necked flask, deionized water is added after the reaction is tracked to the end point by adopting thin layer chromatography, extraction is carried out for 3 times by adopting ethyl acetate, organic phases are combined and dried by anhydrous magnesium sulfate for 24 hours, and after filtration and column chromatography separation, 0.31g of yellow powder is obtained, and the yield is 90%.
(2) 0.3412 g (1mmol) of the yellow solid product in the step (1) and 20mL of toluene are weighed in a 50mL round-bottom flask, the temperature of a reaction system is controlled at-20 ℃, 1mL of diisobutylaluminum hydride of 2.5 mol/L is added under the argon condition, the reaction is stopped after 12 hours, the pH is adjusted to 1 by 10% hydrochloric acid, the mixture is filtered, and the yellow solid is obtained after drying, wherein the yield is 80 percent (the compound 2 in the reaction route).
(3) Weighing 0.37 g (1mmol) of the yellow solid product in the step (2), 0.1118 g (1mmol) of 4-tert-butylaniline, 0.2082 g (1mmol) of phenanthrenequinone, 1.322 g (16 mmol) of ammonium acetate and 60 mL of acetic acid in a 100mL round-bottom flask under the condition of argon, refluxing for 48 hours, adding deionized water, extracting for 3 times by using ethyl acetate, combining organic phases, drying for 24 hours by using anhydrous magnesium sulfate, filtering, and separating by using column chromatography to obtain 0.3133 g with the yield of 80%.
Example 4:
(1) 1.8339g (6mmol) of 4-di-p-toluidino benzaldehyde, 1.6950g (6mmol) of potassium tert-butoxide, 20mL of dimethyl sulfoxide, 6mL (6.6mmol) of diethyl (4-cyanobenzyl) phosphonate and 6mL (6.6mmol) of diethyl (4-cyanobenzyl) phosphonate are weighed into a 50mL three-necked flask, deionized water is added after the reaction is ended by thin layer chromatography, extraction is carried out for 3 times by ethyl acetate, organic phases are combined and dried for 24 hours by anhydrous magnesium sulfate, and separation is carried out by column chromatography after filtration to obtain 1.05g of yellow powder with the yield of 86%.
(2) 0.8063 g (1mmol) of the yellow solid product in the step (1) is weighed, 20mL of toluene is placed in a 50mL round-bottom flask, the temperature of a reaction system is controlled to be-30 ℃ under the argon condition, 3mL of diisobutylaluminum hydride of 2.5 mol/L is added, the reaction is stopped after 12 hours, the pH is adjusted to 2 by 10% hydrochloric acid, the filtration is carried out, and the drying is carried out, so that 0.65 g of yellow solid (the compound 2 in the reaction route) is obtained, and the yield is 80%.
(3) 0.4051 g (1mmol) of the yellow solid product in the step (2), 0.1338 g (1.2mmol) of 4-fluoroaniline, 0.2082 g (1mmol) of phenanthrenequinone, 1.3221 g (16 mmol) of ammonium acetate and 60 mL of acetic acid are weighed in a 100mL round-bottom flask under the argon condition, after reflux reaction for 48 hours, deionized water is added, ethyl acetate is used for extraction for 3 times, organic phases are combined and dried for 24 hours by anhydrous magnesium sulfate, and after filtration and column chromatography separation, 0.5123 g is obtained, and the yield is 73%.
Example 5:
(1) weighing 3.5g (9mmol) of 4- (9H-4 ', 4' -di-tert-butylcarbazole) benzaldehyde, 1.1g (9mmol) of potassium tert-butoxide, 180mL of dimethyl sulfoxide and 9mL (9.6mmol) of diethyl (4-cyanobenzyl) phosphonate in a 500mL three-necked flask, tracking the reaction by thin layer chromatography, adding deionized water after reaching the end point, extracting for 3 times by ethyl acetate, combining organic phases, drying for 24 hours by using anhydrous magnesium sulfate, filtering, and separating by using column chromatography to obtain 3.2g of light yellow powder with the yield of 73%.
(2) Weighing 0.96 g (2 mmol) of the light yellow solid product in the step (1), 20mL of toluene in a 50mL round-bottom flask, controlling the temperature of a reaction system at-50 ℃, adding 2.4 mL of diisobutylaluminum hydride at 2.5 mol/L under the argon condition, reacting for 12 hours, stopping the reaction, adjusting the pH to 3 by using 10% hydrochloric acid, filtering, and drying to obtain 0.69 g of yellow solid (compound 2 in the reaction route), wherein the yield is 71%.
(3) Weighing 0.485 g (1mmol) of the yellow solid product in the step (2), 0.15 g (1.2mmol) of 4-fluoromethylaniline, 0.2082 g (1mmol) of phenanthrenequinone, 1.322 g (16 mmol) of ammonium acetate and 60 mL of acetic acid in a 100mL round-bottom flask under the condition of argon, refluxing for 48 h, adding deionized water, extracting for 3 times by using ethyl acetate, combining organic phases, drying for 24 h by using anhydrous magnesium sulfate, filtering, and separating by using column chromatography to obtain 0.6 g, wherein the yield is 77%.
Example 6:
(1) weighing 3.45g (10.4mmol) of 4- (9H-4 ', 4' -methoxy carbazole) benzaldehyde, 1.17g (10.4mmol) of potassium tert-butoxide, 200mL of dimethyl sulfoxide and 2.93g (11.6mmol) of diethyl (4-cyanobenzyl) phosphonate in a 500mL three-necked flask, tracking the reaction by thin layer chromatography, adding deionized water after reaching the end point, extracting for 3 times by ethyl acetate, combining organic phases, drying for 24 hours by anhydrous magnesium sulfate, filtering, and separating by column chromatography to obtain 3.8g of yellow-green powder with the yield of 85%.
(2) Weighing 0.86 g (2 mmol) of the medium yellow green solid product in the step (1), 20mL of toluene in a 50mL round-bottom flask, controlling the temperature of a reaction system at-40 ℃, adding 3mL of diisobutylaluminum hydride of 2.5 mol/L under the argon condition, reacting for 12 hours, stopping the reaction, adjusting the pH to 5 by using 10% hydrochloric acid, filtering, and drying to obtain 0.30 g of yellow solid (a compound 2 in the reaction route), wherein the yield is 80%.
(3) Weighing 0.434 g (1mmol) of the yellow solid product in the step (2), 0.147g (1mmol) of 4-methoxyaniline, 0.2082 g (1mmol) of phenanthrenequinone, 1.322 g (16 mmol) of ammonium acetate and 60 mL of acetic acid in a 100mL round-bottom flask under the condition of argon, refluxing for 48 hours, adding deionized water, extracting for 3 times by using ethyl acetate, combining organic phases, drying for 24 hours by using anhydrous magnesium sulfate, filtering, and separating by using column chromatography to obtain 0.55 g, wherein the yield is 76%.
Example 7:
this example illustrates the application of the styryl group-containing phenanthroimidazole compound prepared in the present invention in an organic/inorganic hybrid LED device excited by ultraviolet light.
The 1W patch LED chip used in this embodiment is a commercially available unpackaged product, and the silica gel used for packaging such chip is also a commercially available product. The styryl group-containing phenanthroimidazole products of example 1 were weighed outE0.3 g of (E) -1- (4 '-triphenylamino) -2- (4', 1 '' -phenyl-4 '' -phenyl-phenanthroimidazole) -ethylene was placed in a total mass of 1.5 g of silica gel encapsulating gum water (wherein 0.3 g of main gum A and 1.2 g of curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. Dispensing a silica gel glue containing a luminescent material on a surface mounted LED chip (1W, unpackaged semi-finished product, 380 nm), and then drying for 1h at 60 ℃ in a drying oven and curing for 2h at 130 ℃. And testing the device performance by adopting a remote LED photoelectric test system after the curing is finished. The device spectrogram is shown in fig. 4, and the light efficiency of the device can reach 20 lm/W.
0.2 g of the styryl-containing phenanthroimidazole compound of example 2 is weighed and placed in 1.5 g of silica gel packaging glue (wherein 0.3 g of the main glue A and 1.2 g of the curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. Dispensing a silica gel glue containing a luminescent material on a surface mounted LED chip (1W, an unpackaged semi-finished product, 365 nm), and then drying for 1h at 60 ℃ in a drying oven and curing for 2h at 130 ℃. After curing is finished, a remote LED photoelectric test system is adopted to test the performance of the device, and the luminous efficiency of the device can reach 10 lm/W.
0.15 g of the styryl-containing phenanthroimidazole compound obtained in example 3 was weighed and placed in 1.5 g of silica gel-filled glue (wherein 0.3 g of the main glue A and 1.2 g of the curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. The silica gel glue containing the luminescent material is dispensed on a surface mounted LED chip (1W, unpackaged semi-finished product, 395 nm), and then dried for 1h at 60 ℃ in a drying oven and cured for 2h at 130 ℃. After the curing is finished, a remote LED photoelectric test system is adopted to test the performance of the device, and the luminous efficiency of the device can reach 13 lm/W.
0.1 g of the styryl-containing phenanthroimidazole compound of example 4 is weighed and placed in 1.5 g of silica gel packaging glue (wherein 0.3 g of the main glue A and 1.2 g of the curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. Dispensing a silica gel glue containing a luminescent material on a surface mounted LED chip (1W, an unpackaged semi-finished product, 300 nm), and then drying for 1h at 60 ℃ in a drying oven and curing for 2h at 130 ℃. After curing is finished, a remote LED photoelectric test system is adopted to test the performance of the device, and the luminous efficiency of the device can reach 10 lm/W.
0.25 g of the styryl-containing phenanthroimidazole compound of example 5 is weighed and placed in 1.5 g of silica gel-filled glue (wherein 0.3 g of the main glue A and 1.2 g of the curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. Dispensing a silica gel glue containing a luminescent material on a surface mounted LED chip (1W, unpackaged semi-finished product, 380 nm), and then drying for 1h at 60 ℃ in a drying oven and curing for 2h at 130 ℃. After the curing is finished, a remote LED photoelectric test system is adopted to test the performance of the device, and the luminous efficiency of the device can reach 17 lm/W.
0.27 g of the styryl-containing phenanthroimidazole compound of example 6 is weighed out and placed in 1.5 g of silica gel-filled glue (wherein 0.3 g of the main glue A and 1.2 g of the curing agent B component). And after stirring uniformly, performing ultrasonic treatment for 30 min to remove bubbles in the system. Dispensing a silica gel glue containing a luminescent material on a surface mounted LED chip (1W, an unpackaged semi-finished product, 365 nm), and then drying for 1h at 60 ℃ in a drying oven and curing for 2h at 130 ℃. After the curing is finished, a remote LED photoelectric test system is adopted to test the performance of the device, and the luminous efficiency of the device can reach 15 lm/W.
Claims (6)
1. A kind of styryl-containing phenanthroimidazole luminescent material is characterized in that: the chemical structure is as follows:
wherein R is1The group is triphenylamine or carbazole derivative;
R2the group is selected from hydrogen, methyl, methoxy, tert-butyl, halogen,One of halogen-substituted methyl groups.
2. The styryl-containing phenanthroimidazole luminescent material as claimed in claim 1, wherein the triphenylamine and carbazole derivative is any one of the structures shown in formula ii:
3. a method for preparing the styryl-containing phenanthroimidazole compound as claimed in claim 1 or 2, wherein the styryl-containing phenanthroimidazole compound is prepared by a Wittig-Honor reaction, a reduction reaction and a debus-radziszewski "one-pot method", and the process is carried out by only three steps: the synthetic route is as follows:
the synthesis steps of the styryl-containing phenanthroimidazole luminescent material are as follows:
step one, substituent (R)1) Formaldehyde (carbonyl compound): diethyl (4-cyanobenzyl) phosphonate: potassium tert-butoxide in a molar ratio of 1-10.4: 1.2-11.6: dissolving the raw materials in a solvent according to a molar ratio of 1.5-10.4 for reaction, monitoring the reaction by a thin layer chromatography method, and purifying a reaction product by column chromatography to obtain a compound 1;
secondly, weighing the compound 1 under the inert gas atmosphere, placing the compound in a three-neck flask, and adding diisobutyl aluminum hydride solution into a reaction system at the temperature of between 77 ℃ below zero and 22 ℃ below zero; the molar ratio of the compound 1 to the diisobutylaluminum hydride is 1-2: 2.5-7.5; monitoring the completion of the reaction through thin layer chromatography, adding an HCl solution to adjust the pH value to 1-5, extracting with ethyl acetate, combining ethyl acetate, drying, and performing rotary evaporation to recover ethyl acetate to obtain a compound 2;
weighing a compound 2, phenanthrenequinone, aniline or carbazole derivatives, mixing ammonium acetate and acetic acid in a three-neck flask to form a reaction system, adopting inert gas for protection, heating to reach the reflux of the reaction system, monitoring the reaction end point by a thin-layer chromatography method, stopping heating, returning the temperature of the reaction system to room temperature, adding deionized water, pouring the solution into a separating funnel, adding an ethyl acetate extraction solution, repeatedly extracting an aqueous phase until the aqueous phase is clear, combining ethyl acetate extraction solutions, and performing column chromatography chromatographic separation to obtain the styryl-containing phenanthroimidazole luminescent material; wherein the mol ratio of the compound 2, the phenanthrenequinone, the aniline or carbazole derivative and the ammonium acetate is 1: 1-1.2: 1: 16.
4. the method for preparing the styryl-containing phenanthroimidazole luminescent material as claimed in claim 3, wherein: the thin layer chromatography method realizes the monitoring of the reaction process through the disappearance and the reappearance of characteristic absorption peaks of carbonyl and cyano in the infrared spectrum.
5. Use of the styryl-containing phenanthroimidazole luminescent material as claimed in claim 1 or 2, wherein: the styryl-containing phenanthroimidazole luminescent material is used in an organic/inorganic hybrid LED device excited by ultraviolet light energy.
6. The use according to claim 5, wherein the wavelength of the ultraviolet light is 300-400 nm.
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