CN115700246A - Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof - Google Patents
Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN115700246A CN115700246A CN202211230535.9A CN202211230535A CN115700246A CN 115700246 A CN115700246 A CN 115700246A CN 202211230535 A CN202211230535 A CN 202211230535A CN 115700246 A CN115700246 A CN 115700246A
- Authority
- CN
- China
- Prior art keywords
- reaction
- deep blue
- luminescent material
- blue luminescent
- xanthene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a spirofluorene xanthene deep blue luminescent material connected by benzene rings and a preparation method thereof. The spirofluorene xanthene deep blue luminescent material is simple to prepare, has a cross structure, has good thermal, electrochemical and spectral stability, and can regulate and control optical properties and electrical properties by changing a photoelectric active group. Therefore, the spirofluorene xanthene deep blue luminescent material has good application prospect in the field of organic photoelectricity.
Description
Technical Field
The invention belongs to a luminescent material and a preparation method thereof, and relates to a spirofluorene xanthene deep blue luminescent material connected by benzene rings and a preparation method thereof, which can be used in the technical fields of organic electrical storage, organic electricity/photoluminescence, photovoltaic cells, organic nonlinear optics, organic laser and the like.
Background
Organic Light Emitting Diodes (OLEDs) have attracted considerable attention in lighting applications and for flat panel displays over the last three decades (appl. Phys. Lett.,1986,48, 183). In 1987, the first generation fluorescent materials successfully realized luminescence, and according to quantum spin statistics, the lowest excited singlet state (S1) had an internal quantum efficiency of only 25% at the maximum when the conventional fluorescent material transits (the lowest excited singlet state (S1) to the ground state (S0)), and further, the maximum external quantum efficiency was determined to be only 5% at the maximum. In the conventional fluorescent material emission, since the inter-system crossing is in the forbidden state, the utilization of 75% of the lowest excited triplet excitons (T1) is not sufficiently performed. Around 2000 years, the emission of the second generation phosphorescent material begins to appear, the phosphorescence emission utilizes the strong spin coupling effect of noble metals (Ir, pt and the like) to realize T1-S0 emission, but the phosphorescence emission needs the noble metal materials, and the manufacturing cost of the device is further increased while the maximum external quantum efficiency is improved. To achieve low cost manufacturing of high efficiency OLED devices, the third generation of delayed fluorescence materials in 2012 realized that 75% of triplet excitons were efficiently utilized on a noble metal-free basis (Nature, 2012,492, 234). Delayed fluorescence mechanisms are roughly divided into three types, namely triplet-triplet minactine (TTA), local hybridization charge transfer (HLCT) and Thermally Activated Delayed Fluorescence (TADF), and the TADF material has the advantages of low cost, high luminous efficiency, environmental friendliness and the like compared with TTA and HLCT material prepared devices, and is a research hotspot rapidly.
TADF receptor materials are favorable for realizing low-cost, high-efficiency OLEDs, wherein the receptor materials can be classified into aminophenyl rings, triazines, diphenylsulfoxides and similar aromatic compounds, adachi et al utilize a classical electron-withdrawing amino fragment and an electron-donating carbazole fragment to connect with a benzene ring as a bridge, and the maximum External Quantum Efficiency (EQE) of the device is 20.9% by changing the connecting position between amino and carbazole or modifying carbazole groups with methyl, benzene rings and the like (sci. Adv.,2018,4, 6). In the TADF-OLED, an Exciplex (Exciplex) type TADF has a very small electron exchange energy, easily realizes carrier transport balance, generates molecular orientation, forms a polarization effect, improves light extraction efficiency, has a low turn-on voltage, and is more advantageous to realize a high-efficiency TADF-OLED than a single-molecule TADF. At present, through adopting TADF type material as substitute for traditional material, the through-channel type exciplex emission between double-reverse system is successfully realized, the EQE is as high as 17.8%, and the starting voltage is as low as 2.4V (adv.mater, 2015,27,2025, adv.funct.mater, 2016,26, 2002). Although the current Exciplex-TADF can achieve 100% exciton utilization, the correlation between the effective Exciplex emission and the structural features of the monomer material molecules (D or a) is not well defined.
In view of the problems of the small molecules, a spirofluorene xanthene (SFX) framework (org.lett., 2006,8, 2787) which is low in price and easy to modify is synthesized by a one-pot method at the early stage, on the basis of breaking through a cheap preparation technology, a series of SFX-based luminescent materials are constructed by introducing photoelectric or transmission groups, the original molecular structure is further modified, a benzene ring is introduced into the SFX framework, and fragments such as an alkyl chain, an alkoxy chain, a carbazole derivative and the like are introduced on the xanthene framework.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a spirofluorene xanthene deep blue luminescent material connected by benzene rings and a preparation method thereof, and provides a spirofluorene xanthene deep blue luminescent material with excellent cross property and photoelectric property transmission property, a preparation method and application thereof, so as to solve the problem of poor transmission property in the field of organic photoelectricity.
Technical scheme
A spirofluorene xanthene deep blue luminescent material connected with benzene rings is characterized in that the structural general formula is as follows:
a preparation method of the spirofluorene xanthene deep blue luminescent material connected by the benzene ring is characterized by comprising the following steps:
step 1: 2-Bromospirofluorenylxanthene 2-BrSFX 2-boronic acid pinacol ester BOSFX was prepared by Miyaura boronation:
step 2:1, 4-bis (spiro [ fluorene-9, 9' -xanthene ] -2-yl) benzene, namely PDSFX, is prepared from 2-boronic acid pinacol ester, namely BOSFX through Suzuki coupling reaction.
The raw materials participating in the Miyaura boronization reaction in the step 1 are calculated according to the parts by weight: 1.00 to 1.10g of compound BrSFX, 0.92 to 1.02g of compound BrSFX, 0.72 to 0.80g of pinacol diboron, 0.36 to 0.40g of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride.
The Miyaura boronation reaction process of the step 1 is as follows: placing a raw material compound BrSFX, pinacol bisboronate, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride in a sealing system, and wrapping a reaction bottle by adopting tinfoil paper. Vacuumizing and blowing nitrogen for 2-3 times, and injecting a solvent 1, 4-dioxane or toluene into a reaction system; stirring in an oil bath, heating for reaction, extracting an organic layer by a dichloromethane yard, separating an aqueous phase from the organic phase, taking the organic phase, removing the aqueous phase by anhydrous magnesium sulfate or anhydrous sodium sulfate, and concentrating by rotary evaporation to remove the solvent; and then, separating and purifying by column chromatography by using an eluent to obtain white solid powder BOSFX.
The raw materials prepared by Suzuki coupling reaction in the step 2 are calculated in parts: 0.50-0.60 g of compound BOSFX, 0.092-0.110g of 1, 4-dibromobenzene and 0.25-0.28 g of palladium tetratriphenylphosphine.
The Suzuki coupling reaction process of the step 2 comprises the following steps: the raw material compounds BOSFX, 1, 4-dibromobenzene and palladium tetratriphenylphosphine are placed in a reaction vessel for sealing, and a reaction bottle is wrapped by tin host paper. Vacuumizing for 2-3 times, injecting an organic phase B into a reaction container, stirring in an oil bath, heating for reaction, adding an aqueous solution A, extracting an organic layer by using a dichloromethane after the stirring reaction is finished, taking an organic phase after the aqueous phase and the organic phase are separated, removing water by using anhydrous magnesium sulfate or anhydrous sodium sulfate, and removing the solvent by rotary evaporation and concentration; then, eluent is adopted to separate and purify by column chromatography to obtain white solid powder PDSFX.
The eluent is a mixed solvent of petroleum ether and dichloromethane with the ratio of 2.
The temperature of the oil bath stirring heating reaction is 90-110 ℃, and the time is 16-24 h.
The application of the spirofluorene xanthene deep blue luminescent material connected by the benzene ring is characterized in that: the luminescent layer is composed of a host material and a doping donor, and the spirofluorene xanthene deep blue luminescent material is used as the host material or guest material.
The application of the spirofluorene xanthene deep blue luminescent material connected by the benzene ring is characterized in that: the spirofluorene xanthene deep blue luminescent material is used for an information storage device, wherein the structure of the storage device is contacted with a low grid top, and sequentially comprises a substrate, a grid electrode, a tunneling layer, an organic semiconductor, a source electrode and a drain electrode, wherein the spirofluorene xanthene deep blue luminescent material is used as a dielectric layer and is prepared by vacuum evaporation, solution spin coating or ink-jet printing.
Advantageous effects
According to the spirofluorene xanthene deep blue luminescent material connected by the benzene ring and the preparation method thereof, photoelectric active groups can be introduced into active sites on a spirocyclic skeleton and a xanthene skeleton, and the spirofluorene xanthene deep blue luminescent material is easy to modify and does not change a cross structure. The spirofluorene xanthene deep blue luminescent material is simple to prepare, has a cross structure, has good thermal, electrochemical and spectral stability, and can regulate and control optical performance and electrical performance by changing a photoelectric active group. Therefore, the spirofluorene xanthene deep blue luminescent material has good application prospect in the field of organic photoelectricity.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
the spirofluorene xanthene type deep blue luminescent material has good thermal, electrochemical and spectral stability, and can realize the regulation and control of optical performance and electrical performance through functional group modification or doping. Therefore, the spirofluorene xanthene type deep blue luminescent material has a good application prospect in the field of organic photoelectricity.
(1) The spirofluorene xanthene skeleton is prepared by one-pot synthesis, and the method is simple to operate and low in cost; the spirofluorene xanthene type deep blue luminescent material has a regular structure, high rigidity and adjustable electronic energy level, is convenient for solution processing, and expands the application range of the material.
(2) The spirofluorene xanthene type deep blue luminescent material has good spectral, thermal and electrochemical stability.
(3) The spirofluorene xanthene type deep blue light emitting material as a host or guest material has excellent device properties such as high maximum external quantum efficiency, lower starting voltage and high device lifetime in an organic light emitting diode (Dyes Pigments,2021,185, 108894).
(4) The spirofluorene xanthene type deep blue luminescent material can perform host-guest interaction with an electron donor or an electron acceptor, and can effectively regulate and control the phase separation of the donor and the acceptor in an organic optoelectronic device through a unique cross structure (dye Pigments,2018,149, 422-429).
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of PDSFX in the present invention
FIG. 2 shows the UV absorption and fluorescence emission spectra of PDSFX in thin film according to the present invention
FIG. 3 is a Maldi-Tof chart of the PDSFX of the present invention.
FIG. 4 is a graph showing the electrochemical stability of PDSFX in the present invention.
FIG. 5 is a graph showing the redox profile of PDSFX in the present invention.
FIG. 6 is a DSC chart of PDSFX in the present invention.
FIG. 7 is a TG map of PDSFX in the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.
The invention discloses a spirofluorene xanthene type luminescent material which has the following structural general formula I:
the invention also discloses a preparation method of the spirofluorene xanthene deep blue luminescent material, which comprises the following steps:
1: in the reaction route, 2-bromospirofluorene xanthene derivatives in the general formula I are subjected to Miyaura boronization reaction and Suzuki coupling reaction to obtain 1, 4-bis (spiro [ fluorene-9, 9' -xanthene ] -2-yl) benzene (PDSFX); the reaction route is shown as the general formula I:
reaction scheme I
The spirofluorene xanthene deep blue luminescent material can be applied to an organic light emitting diode, wherein the structure of a light emitting diode device is transparent anode/light emitting layer/electron injection layer/cathode, the light emitting layer is composed of a host material and a doping donor, and the spirofluorene xanthene deep blue luminescent material is used as the host material or a guest material.
The spirofluorene xanthene deep blue luminescent material can be applied to an information storage device, wherein the structural low grid top of the storage device is contacted, and the spirofluorene xanthene deep blue luminescent material is used as a dielectric layer and is prepared in a vacuum evaporation, solution spin coating or ink-jet printing mode, wherein the spirofluorene xanthene deep blue luminescent material can be used as a substrate, a grid electrode, a tunneling layer, an organic semiconductor, a source electrode and a drain electrode in sequence.
PDSFX was prepared as follows:
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX):
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX) by Miyaura boronation reaction as follows: the two-neck flask, the magneton and the condenser tube are assembled, the sealing system only leaves a sample adding port, and the refined 1, 4-dioxane is bubbled to remove air in the sample adding port. The starting compound BrSFX (1.00g, 2.44mmol), pinacol diboron (0.92g, 3.62mmol), potassium acetate (0.72g, 7.32mmol), 1' -bis-diphenylphosphinoferrocene palladium dichloride (0.36g, 0.48mmol) were added to the flask, the system was sealed, and the flask was wrapped with tinfoil. The nitrogen is pumped for 2-3 times in a vacuum drum, and 5mL1, 4-dioxane or toluene is injected into a reaction bottle as a solvent required by the reaction. Heating in oil bath at 105 deg.C under stirring for 24 hr, extracting organic layer with dichloromethane, separating water phase from organic phase, removing water with small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and concentrating by rotary evaporation to remove solvent. Then, a mixed solvent of petroleum ether and dichloromethane (2, v/v) is prepared as an eluent, and the white solid powder BOSFX 0.8g is obtained through column chromatography separation and purification, and the yield is 75%. 1 H NMR(400MHz,CDCl 3 ,o[ppm]):7.86-7.88(d,J＝8Hz,1H),7.81-7.83,(d,J＝8Hz,2H),7.59(s,1H),7.34-7.37(t,J＝12Hz,1H),7.22(s,1H),7.21(s,1H),7.20(s,1H),7.17-7.19(dd,J＝8Hz,2H),7.14-7.12(d,J＝8Hz,1H),6.73-6.77(t,J＝16Hz,2H),6.36-6.38(dd,J＝8Hz,2H).1.29(s,12H)。
Preparation of 1, 4-bis (spiro [ fluorene-9, 9' -xanthen ] -2-yl) benzene (PDSFX) from 2-boronic acid pinacol ester (BOSFX):
preparing a mixed solution A of 2mol/L of potassium carbonate and potassium fluoride, 5mL of which provides a reaction alkaline environment, V Tetrahydrofuran (THF) :V Toluene 15mL of a mixed solution B of =1 as a reaction organic solvent, and N was applied to the solutions a and B 2 Bubbling for 2h. The two-mouth flask, the magneton and the condenser tube are assembled, and only the sample adding port is reserved in a sealing system. The starting compounds BOSFX (0.50g, 0.86mmol), 1, 4-dibromobenzene (0.092g, 0.39mmol) and palladium tetratriphenylphosphine (0.25g, 0.22mmol) were added to the flask, the system was sealed, and the flask was wrapped with tin bath paper. Vacuum was applied 2-3 times and 15mL of organic phase B was injected into the reaction flask. 90 ℃ oilThe reaction was heated with stirring, and after 30min, 5mL of aqueous solution A was added. The reaction was stirred. After the reaction is finished, an organic layer is extracted by a dichloromethane yard, after an aqueous phase and the organic phase are separated, the organic phase is taken, a small amount of water is removed by using a small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and the solvent is removed by rotary evaporation and concentration. Then, a mixed solvent of petroleum ether and dichloromethane (5, v/v) was prepared as an eluent, and the mixture was separated and purified by column chromatography to obtain white solid powder PDSFX 0.18g, with a yield of 61%. 1 H NMR(400MHz,CDCl 3 ,o[ppm]) δ 7.84 (dd, J =14.4,7.8hz, 4h), 7.58 (d, J =8.8hz, 2h), 7.47 (d, J =8.6hz, 4h), 7.38 (dd, J =18.9,7.7hz, 8h), 7.21 (dd, J =11.7,4.7hz, 11h), 6.79 (t, J =7.2hz, 4h), 6.46 (d, J =7.7hz, 4h). As shown in fig. 1, the nmr spectrum of PDSFX of the present invention was measured using a nmr apparatus of Bruker 400plus at 295K, and the solvent used for the measurement was deuterated chloroform (CDCl) (CDCl 400 plus) 3 ). FIG. 3 is a time-of-flight mass spectrum of PDSFX of the present invention, the model of the apparatus is Bruker ultra-flex (MALDI-TOF/TOF). The success of the preparation of the PDSFX is proved from the molecular weight, the hydrogen environment and the chemical shift layer.
Example 2:
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX):
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX) by Miyaura boronation reaction as follows: assembling the two-mouth flask, the magneton and the condenser tube, sealing the system and only reserving the sample adding port, and simultaneously bubbling the refined 1, 4-dioxane to remove the air in the flask. 1.05g of the compound BrSFX, 1.0g of pinacol diboride, 0.75g of potassium acetate and 0.38g of 1,1' -bisdiphenylphosphinoferrocene palladium dichloride were added as starting materials to the flask, the system was sealed and the flask was wrapped with tinfoil. Vacuumizing and blowing nitrogen for 2-3 times, and injecting 5mL1, 4-dioxane or toluene serving as a solvent required by the reaction into a reaction bottle. Heating in 110 deg.C oil bath under stirring for 24 hr, extracting organic layer with dichloromethane after reaction, separating water phase and organic phase, removing water with small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and concentrating by rotary evaporation to remove solvent. Then preparing a mixed solvent of petroleum ether and dichloromethane (2, v/v) as an eluent, and separating and purifying by column chromatography to obtain white solid powder BOSFX.
Preparation of 1, 4-bis (spiro [ fluorene-9, 9' -xanthen ] -2-yl) benzene (PDSFX) from 2-boronic acid pinacol ester (BOSFX):
preparing a mixed solution A of 2mol/L of potassium carbonate and potassium fluoride, 5mL providing a reaction alkaline environment, V Tetrahydrofuran (THF) :V Toluene 15mL of a mixed solution B of =1 2 Bubbling for 2h. The two-mouth flask, the magneton and the condenser tube are assembled, and only the sample adding port is reserved in a sealing system. The starting material 0.55g of the compound BOSFX, 0.1g of 1, 4-dibromobenzene and 0.27g of palladium tetratriphenylphosphine were added to the flask, the system was sealed and the reaction flask was wrapped with tin bath paper. Vacuum was applied 2-3 times and 15mL of organic phase B was injected into the reaction flask. The reaction was heated in an oil bath at 100 ℃ with stirring, and after 30min 5mL of aqueous solution A was added. The reaction was stirred. After the reaction is finished, an organic layer is extracted by a methylene dichloride hospital, after a water phase and the organic phase are separated, the organic phase is taken, a small amount of water is removed by using a small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and the solvent is removed by rotary evaporation and concentration. Then, a mixed solvent of petroleum ether and dichloromethane (5, v/v) is prepared as an eluent, and white solid powder PDSFX is obtained through column chromatography separation and purification.
Example 3:
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX):
preparation of 2-boronic acid pinacol ester (BOSFX) from 2-bromospirofluorene xanthene (BrSFX) by Miyaura boronation reaction as follows: assembling the two-mouth flask, the magneton and the condenser tube, sealing the system and only reserving the sample adding port, and simultaneously bubbling the refined 1, 4-dioxane to remove the air in the flask. 1.10g of the compound BrSFX, 1.0g of pinacol diboron, 0.80g of potassium acetate and 0.40g of 1,1' -bisdiphenylphosphinoferrocene palladium dichloride were added as starting materials to a flask, the system was sealed, and the flask was wrapped with tinfoil. Vacuumizing and blowing nitrogen for 2-3 times, and injecting 5mL1, 4-dioxane or toluene serving as a solvent required by the reaction into a reaction bottle. Heating in 110 deg.C oil bath under stirring for 20 hr, extracting organic layer with dichloromethane, separating water phase and organic phase, removing water with small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and concentrating by rotary evaporation to remove solvent. Then preparing a mixed solvent of petroleum ether and dichloromethane (2, v/v) as an eluent, and separating and purifying by column chromatography to obtain white solid powder BOSFX.
Preparation of 1, 4-bis (spiro [ fluorene-9, 9' -xanthen ] -2-yl) benzene (PDSFX) from 2-boronic acid pinacol ester (BOSFX):
preparing a mixed solution A of 2mol/L of potassium carbonate and potassium fluoride, 5mL providing a reaction alkaline environment, V Tetrahydrofuran (THF) :V Toluene 15mL of a mixed solution B of =1 2 Bubbling for 2h. And assembling the two-mouth flask, the magneton and the condenser tube, and only reserving a sample adding port in a sealing system. The starting compounds 0.60g of BOSFX, 0.110g of 1, 4-dibromobenzene and 0.28g of palladium tetratriphenylphosphine were added to the flask, the system was sealed and the reaction flask was wrapped with tin bath paper. Vacuum was applied 2-3 times and 15mL of organic phase B was injected into the reaction flask. The reaction was heated in an oil bath at 100 ℃ with stirring, and after 30min 5mL of aqueous solution A was added. The reaction was stirred. After the reaction is finished, an organic layer is extracted by a dichloromethane yard, after an aqueous phase and the organic phase are separated, the organic phase is taken, a small amount of water is removed by using a small amount of anhydrous magnesium sulfate or anhydrous sodium sulfate, and the solvent is removed by rotary evaporation and concentration. Then preparing petroleum ether and dichloromethane (5, 1, v/v) mixed solvent as an eluent, and separating and purifying by column chromatography to obtain white solid powder PDSFX
The luminescent material belongs to a classical cross structure and has a certain torsion angle and rigidity. On the basis of the material structure, different photoelectric active groups are introduced to obtain a series of spirofluorene xanthene type deep blue luminescent materials (Dyes Pigments,2021,185,108894, dyes Pigments,2018,149, 422-429).
The spirofluorene xanthene type deep blue luminescent material has the following characteristics:
(1) The raw materials are cheap and easy to obtain, and the cost is low;
(2) The reaction condition is mild and the operation is easy;
(3) The rigid structure had spectral stability as shown in fig. 2, the uv absorption and fluorescence emission spectra in pdsfx and film, and the test instruments were a LAMBDA 35 uv spectrophotometer and a RF-6000Plus type spectrometer. The neat film sample was prepared as a 10mg/mL toluene solution at room temperature and then spin-coated on a quartz plate for testing.
(4) The electrochemical properties are stable, cyclic voltammetry curves obtained by continuous 10 times of tests are basically consistent, as shown in fig. 4 and fig. 5, the cyclic voltammetry is used for measuring in a CHI660 electrochemical workstation by adopting a three-electrode system, wherein a working electrode, a counter electrode and a reference electrode are respectively a Pt electrode, a platinum carbon electrode and an Ag/Ag + electrode, an electrolyte is tetrabutylammonium hexafluorophosphate, an oxidation part solvent is an ultra-dry dichloromethane solution, a reduction part solvent is an ultra-dry tetrahydrofuran solution, and the scanning speed is 0.1V/s.
(5) The thermal stability is good, as shown in FIG. 6 and FIG. 7, the differential thermal analysis Data (DSC) is measured by Shimadzu DSC-60A under the protection of nitrogen, and the dosage is 5mg; thermogravimetric data (TGA) were also determined under nitrogen atmosphere from DTG-60H at 5mg. The melting point of the material is 445 ℃, the thermal decomposition temperature is 458 ℃, and the temperature required by preparing a device by vacuum evaporation is met. Therefore, the deep blue luminescent material has good research prospect in the photoelectric field.
By nuclear magnetic resonance hydrogen spectroscopy ( 1 H NMR), time-of-flight mass spectrometry (MALDI-Tof MS), etc., to characterize the structure of spirofluorene xanthene type luminescence. The thermal stability of the materials is tested through thermogravimetric analysis and differential thermal analysis, the electrochemical properties of the materials are characterized through cyclic voltammetry, and the spectral stability of the materials is tested through a thin film high-temperature annealing mode.
The test of the spirofluorene xanthene deep blue luminescent material by the means shows that the spirofluorene xanthene deep blue luminescent material has good electrochemical stability, spectral stability and thermodynamic stability. The spirofluorene xanthene deep blue luminescent material has adjustable band gap and intramolecular accumulation effect, and can be used as a high-efficiency main material, a hole transport material or an electron transport material. The cross and solution processing characteristics of the spirofluorene xanthene deep blue luminescent material can be used for host-guest chemistry and organic field effect transistor memories. The spirofluorene xanthene deep blue luminescent material can also be applied to the fields of sensing, organic electroluminescence, organic photoluminescence, organic photovoltaic cells, organic nonlinear optics, organic laser and the like.
Claims (10)
1. A spirofluorene xanthene deep blue luminescent material connected with benzene rings is characterized in that the structural general formula is as follows:
2. a method for preparing the spirofluorene xanthene deep blue luminescent material connected by the benzene ring in claim 1 is characterized by comprising the following steps:
step 1: 2-Bromospirofluorenylxanthene 2-BrSFX 2-boronic acid pinacol ester BOSFX was prepared by Miyaura boronation:
step 2:1, 4-bis (spiro [ fluorene-9, 9' -xanthene ] -2-yl) benzene, namely PDSFX, is prepared from 2-boronic acid pinacol ester, namely BOSFX through Suzuki coupling reaction.
3. The method of claim 2, wherein: in the step 1, the raw materials participating in the Miyaura boronization reaction are calculated according to the parts by weight: 1.00 to 1.10g of compound BrSFX, 0.92 to 1.02g of compound BrSFX, 0.72 to 0.80g of pinacol diboron, 0.36 to 0.40g of 1,1' -bis-diphenylphosphine ferrocene dichloropalladium.
4. The method of claim 2, wherein: the Miyaura boronization reaction process in the step 1 comprises the following steps: placing a raw material compound BrSFX, diboronic acid pinacol ester, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride in a sealing system, and wrapping a reaction bottle by adopting tinfoil paper. Vacuumizing and blowing nitrogen for 2-3 times, and injecting a solvent 1, 4-dioxane or toluene into a reaction system; stirring in an oil bath, heating for reaction, extracting an organic layer by a dichloromethane yard, separating an aqueous phase from the organic phase, taking the organic phase, removing the aqueous phase by anhydrous magnesium sulfate or anhydrous sodium sulfate, and concentrating by rotary evaporation to remove the solvent; and then, separating and purifying by column chromatography by using an eluent to obtain white solid powder BOSFX.
5. The method of claim 2, wherein: the raw materials prepared by Suzuki coupling reaction in the step 2 are calculated in parts: 0.50 to 0.60g of the compound BOSFX, 0.092 to 0.110g of 1, 4-dibromobenzene and 0.25 to 0.28g of tetrakistriphenylphosphine palladium.
6. The method of claim 2, wherein: the Suzuki coupling reaction process of the step 2 comprises the following steps: the raw material compounds BOSFX, 1, 4-dibromobenzene and palladium tetratriphenylphosphine are placed in a reaction vessel for sealing, and a reaction bottle is wrapped by tin host paper. Vacuumizing for 2-3 times, injecting an organic phase B into a reaction container, stirring in an oil bath, heating for reaction, adding an aqueous solution A, extracting an organic layer by using a dichloromethane after the stirring reaction is finished, separating a water phase from the organic phase, taking the organic phase, removing water by using anhydrous magnesium sulfate or anhydrous sodium sulfate, and removing the solvent by rotary evaporation and concentration; then, eluent is adopted to separate and purify by column chromatography to obtain white solid powder PDSFX.
7. The method according to claim 4 or 6, characterized in that: the eluent is a mixed solvent of petroleum ether and dichloromethane with the ratio of 2.
8. The method according to claim 4 or 6, characterized in that: the temperature of the oil bath stirring heating reaction is 90-110 ℃, and the time is 16-24 h.
9. Use of the benzene ring-linked spirofluorene xanthene deep blue luminescent material according to claim 1, wherein: the spirofluorene xanthene deep blue luminescent material is used for an organic light emitting diode, wherein the structure of the light emitting diode device is transparent anode/luminescent layer/electron injection layer/cathode, the luminescent layer is composed of a host material and a doping donor, and the spirofluorene xanthene deep blue luminescent material is used as the host material or an object material.
10. Use of the benzene ring-linked spirofluorene xanthene deep blue luminescent material according to claim 1, wherein: the structure of the memory device is contacted with the lower grid top, and sequentially comprises a substrate, a grid electrode, a tunneling layer, an organic semiconductor, a source electrode and a drain electrode, wherein the spirofluorene xanthene deep blue luminescent material is used as a dielectric layer and is prepared by vacuum evaporation, solution spin coating or ink-jet printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211230535.9A CN115700246A (en) | 2022-10-09 | 2022-10-09 | Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211230535.9A CN115700246A (en) | 2022-10-09 | 2022-10-09 | Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115700246A true CN115700246A (en) | 2023-02-07 |
Family
ID=85120858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211230535.9A Pending CN115700246A (en) | 2022-10-09 | 2022-10-09 | Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115700246A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710399A (en) * | 2013-12-11 | 2015-06-17 | 方圆环球光电技术盐城有限公司 | Novel blue light-emitting material and preparation thereof |
| CN109535131A (en) * | 2018-12-25 | 2019-03-29 | 西安瑞联新材料股份有限公司 | It is a kind of using cyanopyridine as the compound of receptor and its application |
| CN109608453A (en) * | 2018-12-25 | 2019-04-12 | 西安瑞联新材料股份有限公司 | One kind is with the compound that 4,7- phenanthroline is receptor and its application |
-
2022
- 2022-10-09 CN CN202211230535.9A patent/CN115700246A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710399A (en) * | 2013-12-11 | 2015-06-17 | 方圆环球光电技术盐城有限公司 | Novel blue light-emitting material and preparation thereof |
| CN109535131A (en) * | 2018-12-25 | 2019-03-29 | 西安瑞联新材料股份有限公司 | It is a kind of using cyanopyridine as the compound of receptor and its application |
| CN109608453A (en) * | 2018-12-25 | 2019-04-12 | 西安瑞联新材料股份有限公司 | One kind is with the compound that 4,7- phenanthroline is receptor and its application |
Non-Patent Citations (1)
| Title |
|---|
| MING-LI SUN ET AL.: "Nondoped deep-blue spirofluorenexanthene-based green organic semiconductors (GOS) via a pot，atom and step economic (PASE) route combining direct arylation with tandem reaction", JOURNAL OF MATERIALS CHEMISTRY C, vol. 3, pages 185 - 187 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108640940A (en) | A kind of stable type boracic organic electroluminescent compounds and its application | |
| CN107021926A (en) | A kind of compound containing azepine spiro fluorene and nitrogenous hexa-member heterocycle and its application on OLED | |
| CN107056783A (en) | A kind of compound containing azepine spiro fluorene and nitrogenous hexa-member heterocycle and its application on organic electroluminescence device | |
| CN108586353A (en) | A kind of luminous organic material and its preparation method and application based on anthracene and its derivative | |
| CN107057681A (en) | A kind of photoelectric material containing xanthene structure and its application in OLED fields | |
| CN109970575B (en) | Organic electroluminescent compounds, their preparation and use | |
| CN107868090A (en) | Contain the organic compound and the electroluminescent device of organic light emission of the fluorenes of 9,9 ' spiral shell two | |
| CN107880058A (en) | A kind of compound containing benzheterocycle and its application in OLED | |
| CN106883218A (en) | A kind of organic compound with equal benzene as core and its application on organic electroluminescence device | |
| CN106432158A (en) | Organic light emitting compound material and application thereof | |
| US11515488B2 (en) | Thermally activated delayed fluorescence material having red, green, or blue color, synthesis method thereof, and application thereof | |
| CN107056763A (en) | A kind of electroluminescent organic material and its application using xanthene as core | |
| CN107043382A (en) | A kind of compound as core using triazine and its application on organic electroluminescence device | |
| CN109575039A (en) | A kind of azines organic compound and its application | |
| CN106684254A (en) | Organic electroluminescent device containing chemical compound with dibenzocycloheptene as its core and the application thereof | |
| CN102807554B (en) | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof | |
| CN111484443A (en) | Anilinocarbazole-based hole transport material and application thereof | |
| CN106478451A (en) | A kind of orange light luminescent material and preparation method thereof | |
| CN110437135A (en) | D-A-D ' type fluorescent chemicals and synthesis, application | |
| CN113861206B (en) | Blue electroluminescent material and synthesis method and application thereof | |
| CN109796442A (en) | A kind of spiro fluorene xanthene type electron transport material and its preparation method and application | |
| CN115700246A (en) | Benzene ring connected spirofluorene xanthene deep blue luminescent material and preparation method thereof | |
| CN111808097B (en) | Solvent yellow 184 derivative and preparation method and application thereof | |
| CN110776434B (en) | Hole transport material based on tetraaryl butadiene and preparation method and application thereof | |
| CN110724105B (en) | Triphenylene nitrogen-containing seven-membered ring compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |