CN110330508B - Macrocyclic unit-based luminescent small molecular material and preparation method and application thereof - Google Patents
Macrocyclic unit-based luminescent small molecular material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic luminescent materials, and particularly relates to a luminescent micromolecule material based on a macrocyclic unit, and a preparation method and application thereof. The micromolecule luminescent material with high thermal stability, excellent electron and hole transmission performance and high fluorescence emission efficiency is obtained by covalently connecting a plurality of aromatic ring units and macrocyclic units with different substitution positions. The luminescent material can be applied to the industrial production of organic electroluminescent displays and cell imaging.
Description
Technical Field
The invention belongs to the field of organic luminescent materials, and particularly relates to a luminescent micromolecule material based on a macrocyclic unit, and a preparation method and application thereof.
Background
Organic electroluminescent diodes (OLEDs), as opposed to Liquid Crystal Displays (LCDs), have received much attention from research institutes and industries due to their advantages of wide viewing angle, active light emission, ground operating voltage, ultra-thin, flexible fabrication, and low power consumption. Currently, OLEDs displays have been used in cell phone screens, and large area OLED televisions have been developed and put on the market. However, the OLED is also limited to be widely used in a large area due to its high price. Therefore, developing a novel luminescent material, improving the device preparation process level and the yield in the device preparation process are important directions for developing the OLED.
In order to realize the light emission of the OLED device, two main types of materials, namely fluorescent materials and phosphorescent materials, can be selected. Although the phosphorescent material has high quantum efficiency and luminous efficiency, the phosphorescent material has high price and short service life, and the like, which limit the wide application of the phosphorescent material in the OLED device. Now, in order to realize OLED color display, researchers mainly focus on the development of red, green, and blue tricolor fluorescent materials with high stability and high luminous efficiency. Through the development of more than 20 years, some high-efficiency fluorescent small molecule materials are reported, such as isatin derivative red light materials (opt. eng.,2011,50(4),044002.), coumarin derivative green light materials (org.lett.,2004,6(8), 1241-yl 1244.), blue light materials trimeric distyrylbenzene (adv.mater.,2005,17(22): 2710-yl 2714), and the like. At present, the small molecule fluorescent material applied to the display field is mainly an evaporation process, but the process is complex, the luminescent material is wasted, the cost is high, and the method is not suitable for the popularization and application of large-area OLED devices. In addition, the polymer electroluminescent device applicable to solution processing seriously affects the application of the luminescent polymer due to the difficulty in purification of the luminescent polymer and the problem of batch reproducibility.
The composition of the luminescent small molecular material needs more research, and further, a more excellent fluorescent luminescent material capable of being processed by solution is developed.
Disclosure of Invention
The polycyclic unit as an excellent aromatic heterocyclic compound has been widely studied and applied in the field of organic electronics due to its advantages of high thermal and optical stability, high fluorescence quantum efficiency, easily modified structure, high electron injection and transmission capability, etc. Therefore, the invention synthesizes novel solution-processable small molecular compounds by introducing macrocyclic units into small molecular luminescent materials, and applies the small molecular materials as luminescent layers in organic electroluminescent devices and cell imaging.
The invention aims to provide design and application of a large-ring small-molecule luminescent material.
The chemical structural formula of the micromolecule luminescent material provided by the invention has the following characteristics:
Ar1，Ar2，Ar3，Ar4，Ar5，Ar6,Ar7，Ar8，Ar9，Ar10，Ar11，Ar12the structures of the two groups can be the same or different; and, Ar1，Ar2，Ar3，Ar4，Ar5，Ar6,Ar7，Ar8，Ar9，Ar10， Ar11，Ar12A structure selected from the group consisting of:
wherein A is S, SO2Se, SeO or SeO2；X＝O，S，Se，Te，NR1，PR1； Y＝O，S，Se，Te，C(R1)2，Si(R1)2，Ge(R1)2,Sn(R1)2,NR1,PR1；R1Is H, C1～C30A linear or branched alkyl group of,
R2Is H, C1～C30Linear or branched alkyl.
The synthesis method of the compound comprises the following steps: and carrying out conjugate coupling reaction on the dibromo seven-membered fused ring compound and aryl boric acid ester, aryl boric acid or aryl tributyl tin compound to obtain a target product.
Synthesis method 1
Dissolving 1 molar equivalent of alkylated dibromo seven-membered fused ring compound in tetrahydrofuran, adding 2-4 molar equivalents of aryl boric acid ester or aryl boric acid and 2-10 molar equivalents of organic or inorganic alkaline water solution in an inert gas environment, stirring, adding 0.01-0.10 molar equivalent of palladium catalyst, raising the temperature to reflux, reacting for 5-24 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, and purifying the filtrate by column chromatography to obtain a product.
Synthesis method II
Dissolving 1 molar equivalent of alkylated dibromo seven-membered fused ring compound in toluene, adding 2-4 molar equivalents of aryl tributyltin compound and 0.01-0.10 molar equivalent of palladium catalyst in an inert gas environment, stirring, raising the temperature to 50-120 ℃, reacting for 5-24 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, and purifying the filtrate by column chromatography to obtain the product.
The preparation method of the alkylated dibromo seven-membered fused ring compound comprises the following steps:
(1) 2,2' - (9, 9-bis (2-ethylhexyl-9H-fluorene-2, 7-diyl) -bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolane), 1-bromo-2- (methyl-sulfinyl) benzene, tetrakis (triphenylphosphine) palladium catalyst, tetrabutylammonium bromide phase transfer catalyst, were completely dissolved in toluene under nitrogen, and then K was injected2CO3Aqueous solution, and reacted at 80 ℃ for 24 hours. Cooling, separating and extracting, washing with water, performing rotary evaporation and purifying to obtain a yellow oily compound 3;
(2) compound 3, trifluoromethanesulfonic acid and phosphorus pentoxide were added to a round bottom flask. The mixture was stirred at room temperature for 12 hours, and then poured into ice water. After collecting the precipitate and drying in vacuo, it was dissolved in pyridine under nitrogen and reacted at 90 ℃ for 8 hours. Cooling, extracting, washing with water, concentrating and purifying. Obtaining a white solid compound 4;
(3) compound 4 was completely dissolved in anhydrous dichloromethane at room temperature, and m-chloroperbenzoic acid was added in three portions. After stirring at room temperature for 8 hours, a saturated aqueous solution of sodium hydroxide was added to terminate the reaction. Extracting, washing, rotary steaming and purifying the mixture to obtain a white solid compound 5;
(4) a solution of N-bromosuccinimide in trifluoroacetic acid and concentrated sulfuric acid was added dropwise to a chloroform/trifluoroacetic acid solution of compound 5 under nitrogen. The reaction mixture was stirred for 12 hours and extracted, washed with water, concentrated, and purified to give an alkylated dibromo seven-membered fused ring compound.
Arylboronic acid esters or arylboronic acids are 1-naphthylboronic acid, 2- (9,9 ' -spirobis [ [ fluorene ] -2-yl ] -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan, 4,5, 5-tetramethyl-2- (9,9,9 ', 9 ' -tetraoctyl-9H, 9 ' H- [2, 2' -difluorofluorene ]) -7-yl) -1,3, 2-dioxaborane, N-diphenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxalan-2-yl) aniline or 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene.
The invention aims to apply the organic light-emitting micromolecule material as a light-emitting layer to an organic electroluminescent device, and the thickness of the light-emitting layer is 10-1000 nanometers.
The organic electroluminescent device structure comprises a substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially stacked; or the organic electroluminescent device structure comprises a substrate, a cathode layer, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer and an anode layer which are sequentially stacked;
the active layer of the organic electroluminescent device is realized by a solution processing method, and comprises spin coating, brush coating, spray coating, dip coating, roll coating, screen printing, printing or ink-jet printing methods.
The invention also aims to prepare organic nano particles from the organic luminescent micromolecule material, and the organic nano particles are used as a fluorescent luminescent material to be applied to biological cell imaging, and the size of the luminescent micromolecule is 1-100 nanometers.
The invention has the advantages and beneficial effects that: provides the design and preparation of a novel large-ring luminescent small molecule, and the novel large-ring luminescent small molecule is used as a luminescent layer to be applied to organic electroluminescent devices and cell imaging. The small molecular compound constructed by the macrocyclic unit and the electron-donating aromatic compound unit has high thermal stability, excellent electron and hole transport performance, high fluorescence emission efficiency and excellent electroluminescent performance, and the luminous efficiency of the small molecular compound exceeds that of the similar molecules.
Drawings
UV-VIS absorption and fluorescence spectra of the compound of FIG. 1 in solution
FIG. 2 ultraviolet-visible absorption and fluorescence spectra of compounds in thin films
FIG. 3 Cyclic voltammogram of a compound
FIG. 4 Voltage-Current Density-Brightness Curve of the Compound
FIG. 5 Current Density-efficiency curves for compounds
FIG. 6 Current Density-external Quantum efficiency curves for compounds
Detailed Description
The following examples are given to illustrate the respective constituent monomers proposed in the present invention, and the present invention is not limited to the following examples.
Example Synthesis of 9, 9-bis (2-ethylhexyl) -2, 7-bis (2-methylsulfinyl) phenyl) -9H-fluorene (Compound 3)
2,2' - (9, 9-bis (2-ethylhexyl-9H-fluorene-2, 7-diyl) -bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) (9.64g, 15mmol, available from Osseki, Guangzhou Co., Ltd.), 1-bromo-2- (methyl-sulfinyl) benzene (7.23g, 33mmol, New J.chem.,2015,39, 6513-2CO3(20.7g, 0.15mol) of an aqueous solution (50 wt%), and reacted at 80 ℃ for 24 hours. After cooling to room temperature, the organic layer was separated, the aqueous layer was extracted with dichloromethane, washed with water and then concentrated on a rotary evaporator, and the crude product was purified by silica gel column chromatography. Petroleum ether/dichloromethane mixture (1: 3 by volume) was used as eluent to give a yellow oil in 51.5% yield (4.52 g).
Example 29, 9-bis (2-ethylhexyl) bis [2, 3-b; synthesis of 6,7-b ] benzo [ d ] thiophene (Compound 4)
9, 9-bis (2-ethylhexyl) -2, 7-bis (2-methylsulfinyl) phenyl) -9H-fluorene (468.9mg, 0.668mmol), trifluoromethanesulfonic acid (4.2mL), and phosphorus pentoxide (254.5mg, 1.336mmol) were charged to a 250mL round bottom flask. The mixture was stirred at room temperature for 12 hours, and then poured into ice water. After collecting the precipitate and drying in vacuo, it was dissolved in 50ml of pyridine under nitrogen and reacted at 90 ℃ for 8 hours. When it was cooled to room temperature, the mixture was extracted with dichloromethane and washed with water, concentrated by rotary evaporator. The crude product was purified by silica gel column chromatography using petroleum ether as eluent. A white solid was obtained in 52% yield (207 mg).
Example 39, 9-bis (2-ethylhexyl) bis [2, 3-b; synthesis of 6,7-b ] benzo [ d ] thiophene-S, S-dioxide (Compound 5)
Reacting 9, 9-bis (2-ethylhexyl) bis [2, 3-b; 6,7-b ] benzo [ d ] thiophene (2.89g, 4.8 mmol) was completely dissolved in 40ml of anhydrous dichloromethane, and m-chloroperbenzoic acid (4.14g, 24mmol) was added in three portions. After stirring at room temperature for 8 hours, a saturated aqueous solution of sodium hydroxide was added to terminate the reaction. The mixture was extracted with dichloromethane and washed with water and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel using a petroleum ether/dichloromethane mixture (volume ratio 2: 1) as eluent. A white solid was obtained in 84% yield (2.69 g).
Example 4 Synthesis of alkylated dibromo seven-membered fused Ring Compound (Compound M1)
Trifluoroacetic acid and concentrated sulfuric acid solution (volume ratio 1: 1, 6ml) of N-bromosuccinimide (NBS, 1.05g, 5.88mmol) were added dropwise to 9, 9-bis (2-ethylhexyl) bis [2,3-b under nitrogen; 6,7-b ] benzo [ d ] thiophene-S, S-dioxide (1.86g, 2.67mmol) in chloroform/trifluoroacetic acid (volume ratio 1: 6, 28 mL). The reaction mixture was stirred for 12 hours, extracted with dichloromethane, washed with water and the organic layer was concentrated. The residue was purified by column chromatography on silica gel using a petroleum ether/dichloromethane mixture (2: 1 by volume) as eluent. Compound M1 was obtained as a white solid in 86% yield (1.89 g).
EXAMPLE 5 Synthesis of FBTO-EHNa Compound
M1(1.65g, 2.0mmol), 1-naphthylboronic acid (1.12g, 4.4mmol) and Pd (PPh)3)4 (115.6mg, 0.1mmol) was placed in a 15mL reaction flask. After evacuation and nitrogen blanketing three times, THF (8mL) and aqueous potassium carbonate (K) were added2CO350 wt%, 8mL) were sequentially poured into a reaction flask, and the mixture was stirred at 75 ℃ for 24 hours. After cooling to room temperature, THF was evaporated and the crude product was purified by silica gel column using petroleum ether/dichloromethane mixed solvent (volume ratio 2: 1) as eluent. FBTO-EHNa was obtained as a pale yellow solid in 68% yield (1.25 g).
EXAMPLE 6 Synthesis of FBTO-EHSF Compound
Synthesis procedure was the same as FBTO-EHNa, using 2- (9, 9' -spirobi [ [ fluorene ] -2-yl ] -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (1.95g, 4.4mmol, available from Osseiki, Guangzhou) instead of 1-naphthylboronic acid, giving FBTO-EHSF as a pale yellow solid in 76% yield (1.97 g).
EXAMPLE 7 Synthesis of FBTO-EHFF Compound
The synthesis was carried out in the same manner as FBTO-EHNa using 4,4,5, 5-tetramethyl-2- (9,9,9 ', 9' -tetraoctyl-9H, 9 'H- [2, 2' -difluorofluorene ]) -7-yl) -1,3, 2-dioxaborane (2.17g, 2.4mmol, available from Osseiki, Guangzhou) instead of 1-naphthylboronic acid. A pale yellow solid of FBTO-EHFF was obtained in 69% yield (1.84 g).
EXAMPLE 8 Synthesis of FBTO-EHTPA Compound
The synthesis was carried out in the same manner as FBTO-EHNa, using N, N-diphenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxolan-2-yl) aniline (1.11g, 3.0mmol, available from Ossa, Guangzhou) in place of 1-naphthylboronic acid. FBTO-EHFF was obtained as a pale yellow solid in 72% yield (1.25 g).
EXAMPLE 9 Synthesis of FBTO-EHF Compound
Synthesis was carried out in the same manner as FBTO-EHNa using 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane) -9, 9-dioctylfluorene (1.03g, 2.0mmol, obtained from Osseki, Guangzhou) in place of 1-naphthylboronic acid. FBTO-EHF was obtained as a pale yellow solid in 78% yield (1.13 g).
The following are examples of the preparation of organic electroluminescent devices
Example 10
Placing an ITO glass substrate on a film developing frame, and ultrasonically cleaning for ten minutes by using a low-concentration semiconductor cleaning solution to remove metal ions which can be adsorbed on the surface of the substrate; ultrasonically cleaning twice with deionized water for ten minutes respectively to remove residual cleaning solution; ultrasonic cleaning with isopropanol for ten minutes to remove water and dry easily; drying in an oven at 80 deg.C; before the device is manufactured, the dried ITO glass substrate is treated by oxygen plasma (O) in an oxygen plasma etching instrument2Plasma) bombardment for twenty minutes.
Through the cleaning steps, impurities on the surface of the ITO glass substrate are fully removed, and the contact angle O in film forming can be improved2The Plasma treatment can further remove residual organic impurities on the surface of the substrate and can further improve the contact angle and the morphology.
The device structure of the light-emitting diode is ITO/PEDOT, PSS/EML/DPEPO/TmPyPB/Liq/Al. First, a hole injection (transport) layer PEDOT, a PSS aqueous dispersion (1% by mass aqueous solution, available from Bayer corporation), was spin-coated on an ITO substrate of an anode conductive glass at high speed by means of a spin coater (KW-4A), to a thickness ofThe degree is determined by the rotation speed, and the film thickness is measured and monitored by a surface profiler (Alpha-Tencor 500 model, Tritek) to be 40 nm. After the film formation, the residual solvent was removed by heat treatment at 140 ℃ for 10 minutes. Small molecule light emitting materials (10 mg per ml) dissolved in chlorobenzene were then spin coated onto PEDOT: and (3) the PSS layer. After thermal annealing at 50 ℃ for 10 minutes, the sample was placed in a vacuum chamber. The hole blocking layer (DPEPO), the electron transport layer (TmPyPB), the electron injection layer (Liq) and the Al cathode were continuously evaporated in a vacuum chamber. In N2The apparatus was sealed with a curable UV resin in an ambient glove box. The EL characteristics of the devices were measured in an air environment after encapsulation. A PR735 SpectraScan spectral radiometer (Photo Research) was combined with a Keithley 2400 source measurement unit and controlled using custom software while determining current-voltage-luminous intensity characteristics and electroluminescent properties such as EL spectra.
The following examples are provided to illustrate the devices and characteristics of the small molecule light emitting material of the present invention, but the present invention is not limited to the examples.
Table 1 thermal and optical data for the Compounds
TABLE 2 electrochemical data for compounds
TABLE 3 electroluminescent device Properties of the Compounds
Claims (6)
1. A luminescent micromolecule material based on macrocyclic units is characterized in that the micromolecule material contains macrocyclic unit cores, and the specific chemical structural formula is as follows:
2. a method for preparing a macrocyclic unit based light-emitting small molecule material according to claim 1, wherein the method comprises the following steps:
dissolving 1 molar equivalent of alkylated dibromo seven-membered fused ring compound in tetrahydrofuran, adding 2-4 molar equivalents of aryl boric acid ester or aryl boric acid and 2-10 molar equivalents of organic or inorganic alkaline water solution into an inert gas environment, stirring, adding 0.01-0.10 molar equivalent of palladium catalyst, raising the temperature to reflux, reacting for 5-24 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, and purifying the filtrate by column chromatography to obtain a product;
or dissolving 1 molar equivalent of alkylated dibromo seven-membered fused ring compound in toluene, adding 2-4 molar equivalents of aryl tributyltin compound and 0.01-0.10 molar equivalent of palladium catalyst in an inert gas environment, stirring, raising the temperature to 50-120 ℃, reacting for 5-24 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, and purifying the filtrate by column chromatography to obtain the product.
3. Use of a macrocyclic unit based light-emitting small molecule material according to claim 1, wherein: the small molecular material is used as a light-emitting layer and applied to an organic electroluminescent device.
4. Use of a luminescent small molecule material according to claim 3, characterized in that: the thickness of the light emitting layer is 10-1000 nanometers.
5. Use of a luminescent small molecule material according to claim 3, characterized in that: the organic electroluminescent device structure sequentially comprises a laminated substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer; or the organic electroluminescent device structure comprises a substrate, a cathode layer, an electron injection layer, an electron transport layer, a luminescent layer, a hole transport layer, a hole injection layer and an anode layer which are laminated in sequence.
6. Use of a luminescent small molecule material according to claim 3, characterized in that: the luminescent layer is realized by a solution processing method, and comprises spin coating, brush coating, spray coating, dip coating, roll coating, screen printing, printing or ink-jet printing methods.
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