CN110183361B - Construction and application of cross-shaped thermal activity delay fluorescent material - Google Patents
Construction and application of cross-shaped thermal activity delay fluorescent material Download PDFInfo
- Publication number
- CN110183361B CN110183361B CN201910506264.7A CN201910506264A CN110183361B CN 110183361 B CN110183361 B CN 110183361B CN 201910506264 A CN201910506264 A CN 201910506264A CN 110183361 B CN110183361 B CN 110183361B
- Authority
- CN
- China
- Prior art keywords
- bpsp
- bpsb
- compound
- thermal activity
- cross
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Abstract
The invention discloses a bis (phenylsulfonyl) benzene-based organic thermal activity delayed fluorescent material and application thereof in a solution processing type organic electroluminescent device. The invention introduces a two-dimensional molecular concept, and respectively introduces triphenylamine, 9-dimethylacridine and phenothiazine donor units into an electron acceptor bis (phenylsulfonyl) benzene unit, thereby constructing a series of 'cross' -shaped thermal activity delayed fluorescent materials. The material is beneficial to separating the space distribution of the highest occupied orbit and the lowest empty orbit of molecules, and smaller energy gap difference between single/triplet states is obtained; and the spatial structure of the material is beneficial to increasing the solubility of the material. The material is used as a dopant of a luminescent layer, and an organic electroluminescent device is prepared by a solution method, so that the maximum external quantum efficiency of up to 20.5 percent is obtained.
Description
Technical Field
The invention relates to a bis (phenylsulfonyl) benzene-containing organic Thermal Activity Delayed Fluorescence (TADF) material, in particular to a Thermal Activity Delayed Fluorescence (TADF) material which takes a bis (phenylsulfonyl) benzene unit as an electron acceptor and takes triphenylamine, 9-dimethylacridine and phenothiazine as electron donors respectively, and an application of the TADF material as a luminescent layer material of a solution processing type organic electroluminescent diode, belonging to the technical field of organic electroluminescent materials.
Technical Field
Thermally Activated Delayed Fluorescence (TADF), referred to as E-delayed fluorescence in the last 60 th century, since they can exploit all singlet states (S) without noble metals (e.g., Ir, Pt, etc.)1) And triplet excitons (T)1) It is of interest to emit light. To date, the most effective strategy for constructing TADF molecules consists of a distorted donor-acceptor (D-a) backbone. Such structures can achieve smaller energy gaps (Δ E) between singlet and triplet states by spatial separation of the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO)ST) And TADF performance is realized. However, the purpose is toMost of the previously reported TADF molecules have one-dimensional structures; most TADF molecules show higher external quantum efficiency only in vacuum evaporation type electroluminescent devices (>20%). Therefore, the development of a novel solution-processed TADF luminescent material has important research significance.
It is well known that two-dimensional materials are widely used in semiconductor materials due to their unique physical and chemical properties, and especially the spatial structure of two-dimensional materials can effectively adjust the band gap of molecules and the solubility of materials. Therefore, the invention introduces a two-dimensional concept into the TADF molecules, constructs a series of TADF molecules with a 'cross' type, and further researches the molecular structure-performance relationship of the TADF molecules. Diphenyl sulfone (DPS) group is widely used as an acceptor unit of TADF molecules because of its good electronegativity and tetrahedral structure. In order to further adjust the molecular properties, researchers have introduced another phenylsulfone unit into the DPS group to form a new acceptor unit bis (phenylsulfonyl) benzene (BPSB), and obtained blue-light TADF materials based on the BPSP acceptor unit with a maximum external quantum efficiency of 24.6%, but they prepared electroluminescent devices by vacuum deposition. Although TADF materials based on BPSB acceptor units have good application prospects in OLEDs, to date, only a few relevant documents have been reported. Based on the reasons, the invention combines the structural characteristics of two-dimensional molecules and the electronic characteristics of BPSB, introduces donor units of triphenylamine, 9-dimethylacridine and phenothiazine to the central benzene ring of the BPSB unit, and constructs series of 'cross' -type TADF molecules of TPA-BPSB, DMAc-BPSB and PTZ-BPSP; further introducing a methyl unit into the molecule to construct TADF molecules MTPA-BPSB, MDMAc-BPSB and MPTZ-BPSB; the molecular structure-performance relationship of the organic electroluminescent device is studied in detail, the organic electroluminescent device is prepared through solution processing, the electroluminescent device with the external quantum efficiency as high as 20.5% is obtained, and a theoretical basis is provided for constructing a high-efficiency two-dimensional TADF material.
Disclosure of Invention
Aiming at the technical defects of shortage of TADF materials, low device efficiency and the like in the solution processing type, the invention aims to provide a 'cross-shaped' type thermal activity delay fluorescent material which takes a bis (phenylsulfonyl) benzene unit as an electron acceptor and takes triphenylamine, 9-dimethylacridine and phenothiazine as electron donors respectively.
Another object of the present invention is to provide a solution-processed organic electroluminescent device having excellent light-emitting properties by using the thermally active delayed fluorescent material as a material for a light-emitting layer of a solution-processed organic electroluminescent diode.
In order to achieve the above technical objects, the present invention provides a thermally active delayed fluorescence material based on a bis (phenylsulfonyl) benzene unit, which has a structure of formula 1 to formula 6:
the 'cross-shaped' type thermal activity delayed fluorescent material has the structural formula 1-6, wherein a bis (phenylsulfonyl) benzene unit is used as an electron acceptor, and triphenylamine, 9-dimethylacridine and phenothiazine are used as electron donors respectively. The structure has a larger space distortion structure, is favorable for separating HOMO and LUMO distribution of molecules, and obtains smaller Delta EST(ii) a Meanwhile, the solubility of the material can be increased, and a high-efficiency solution processing type TADF material is obtained.
On the other hand, the invention also provides application of the ' cross-shaped ' type thermal activity delay fluorescent material, and the cross-shaped ' type thermal activity delay fluorescent material is used as a light-emitting layer material of an organic light-emitting diode and is used for a solution processing type organic light-emitting device. The device obtains the maximum external quantum efficiency of 20.5 percent
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention introduces a two-dimensional concept into TADF molecules for the first time to construct a 'cross-shaped' type thermal activity delay fluorescent material. The material has larger space to separate a donor unit from an acceptor unit, which is favorable for separating HOMO and LUMO distribution of molecules to obtain smaller Delta EST(ii) a And the space structure of the material is beneficial to increasing the solubility of the material, and a high-efficiency solution processing type organic electroluminescent device is obtained. The invention is toWhen the 'cross-shaped' type thermal activity delay fluorescent material is used as a luminescent layer material of a solution processing type organic electroluminescent diode, the maximum external quantum efficiency of the device is 20.5 percent, which is the highest efficiency of the TADF material based on the bis (phenylsulfonyl) benzene unit in the solution processing type organic electroluminescent device at present.
Drawings
FIG. 1 is a graph showing the thermogravimetric curves of TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB compounds obtained in example 1 of the present invention.
FIG. 2 shows a toluene solution of TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP compounds obtained in example 1 of the present invention (10)-5M) ultraviolet-visible absorption spectrum.
FIG. 3 shows a toluene solution of TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP compounds obtained in example 1 of the present invention (10)-5M) fluorescence spectrum.
FIG. 4 is a graph showing transient attenuation curves of the compounds TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP obtained in example 1 of the present invention in a PMMA thin film.
FIG. 5 is a graph showing the external quantum efficiency-current density curves (inset: electroluminescence spectrum) for different doping concentrations of TPA-BPSP, a compound prepared in example 1 of the present invention.
FIG. 6 is a graph of luminance-voltage-current density curves for different doping concentrations of the TPA-BPSP compound prepared in example 1 of the present invention.
FIG. 7 is an external quantum efficiency-current density curve (inset: electroluminescence spectrum) of the compound MTPA-BPSP prepared in example 1 of the present invention with different doping concentrations.
FIG. 8 is a graph of luminance-voltage-current density curves of the compound MTPA-BPSP prepared in example 1 of the present invention at different doping concentrations.
Detailed Description
The following specific examples are intended to further illustrate the invention, but these specific embodiments do not limit the scope of the invention in any way.
Example 1
The reaction conditions are a) cuprous iodide, anhydrous potassium carbonate and dimethyl sulfoxide, and the reaction temperature is 120 ℃ for 24 hours; b) hydrogen peroxide and acetic acid are refluxed for 18 hours; c) refluxing cuprous chloride, potassium hydroxide and toluene for 24 hours; d) n-butyl lithium, isopropanol pinacol borate and tetrahydrofuran, at-78 ℃ for 12 hours; e) tetrakis (triphenylphosphine) palladium, anhydrous potassium carbonate, tetrahydrofuran, 80 ℃ for 24h
Synthetic route to example 1
Synthesis of Compound 1:
diphenyldisulfide (932mg,4.27mmol), 1, 4-dibromo-2, 5-diiodobenzene (2.00g,3.89mmol), cuprous iodide (222mg,1.16mmol), anhydrous potassium carbonate (1.34g,9.70mmol), and 100mL of dimethyl sulfoxide were added sequentially to a 200mL single-necked flask, and the mixture was stirred at 120 ℃ for 24h under nitrogen. After the reaction liquid is cooled to room temperature, pouring the reaction liquid into ice water; the mixture was extracted with dichloromethane (3X 30mL) and the organic layer was collected; the organic layer was washed with water (250mL), dried, filtered, and distilled under reduced pressure to remove the solvent; the crude product was separated by column chromatography using petroleum ether as eluent to give 500mg of a white solid with a yield of 43%.1H NMR(400MHz,CDCl3)δ7.42(m,10H),7.06(s,2H).
Synthesis of compound M1:
compound 1(4.50g,9.95mmol) and 150mL of glacial acetic acid were added to a 250mL two-necked flask, heated to 100 ℃ and then 10mL of 30% hydrogen peroxide solution was dropped into the reaction system and stirred for 18 hours. After the reaction solution was cooled to room temperature, the reaction solution was poured into 500mL of ice water, and the precipitate was filtered off and recrystallized from ethanol to give 3.55g of a white solid with a yield of 66%.1H NMR(400MHz,CDCl3)δ8.61(s,2H),7.97-7.95(m,4H),7.68(t,J＝8.0Hz,2H),7.56(t,J＝8.0Hz,4H).
Synthesis of Compound 2:
to a 250mL single neck flask were added 9, 9-dimethylacridine (5.0g,24.7mmol), 2-bromo-5-iodobenzene (9.06g,32.1mmol), cuprous chloride (489mg,4.94mmol), potassium hydroxide (6.92g,124mmol), 1, 10-phenanthroline (891mg,4.94mmol), and 130mL of toluene in that order, and the mixture was 12 g under nitrogenStirred at 0 ℃ for 24 h. After the reaction solution was cooled to room temperature, dichloromethane (3 × 30mL) was extracted, and the organic layer was washed with brine (3 × 30mL), dried, filtered, and distilled under reduced pressure to remove the solvent; the crude product was separated by column chromatography using petroleum ether as eluent to give 4.78g of a white solid in 53% yield.1H NMR(300MHz,CDCl3)δ7.77-7.74(m,2H),7.47-7.44(m,2H),7.25-7.21(m,2H),7.0-6.91(m,4H),6.26-6.23(m,2H),1.68(s,6H).
Synthesis of compound M2:
compound 2(5.00g,13.7mmol) and 150mL of anhydrous tetrahydrofuran were added to a 250mL two-necked flask, stirred at-78 ℃ for 30 minutes under nitrogen, followed by dropwise addition of n-butyllithium (2.5M,7.14mL,17.8mmol) to the reaction mixture, reaction for 1 hour, isopropanol pinacol borate (3.83g,20.6mmol) was added dropwise to the reaction mixture, and after reaction for 2 hours, the mixture was allowed to stand at room temperature overnight. The reaction was terminated and 20mL of water was added to quench the reaction. The reaction solution was extracted with dichloromethane (3X 30mL), and the organic layer was washed with water (250mL), dried, filtered, and distilled under reduced pressure to remove the solvent; the crude product was isolated by column chromatography using petroleum ether and dichloromethane (V: V ═ 10:1) as eluent to give 5.72g of a white solid in 78% yield.1H NMR(400MHz,CDCl3)δ8.06(d,J＝8.0Hz,2H),7.45(dd,J＝1.9Hz,7.4Hz,2H),7.35(d,J＝12Hz,2H),6.93(m,4H),6.25(dd,J＝1.6Hz,7.8Hz,2H),1.69(s,6H),1.40(s,12H).
Synthesis of Compound 3:
the synthesis procedure was similar to compound 2, and the crude product was isolated by column chromatography using petroleum ether as eluent to give 3.95g of a white solid with 25% yield.1H NMR(400MHz,CDCl3)δ7.35(d,J＝8.0Hz,1H),7.27-7.22(m,4H),7.07-7.00(m,6H),6.95(d,J＝4.0Hz,1H),6.77(dd,J＝2.7Hz,8.0Hz,1H),2.28(s,3H).
Synthesis of compound M3:
the synthesis procedure was similar to compound M2 and the crude product was isolated by column chromatography using petroleum ether dichloromethane (V: V ═ 10:1) as eluent to give 2.78g of a white solid in 62% yield.1H NMR(400MHz,CDCl3)δ7.63(d,J＝8.0Hz,1H),7.26-7.22(m,4H),7.09(dd,J＝1.1Hz,8.6Hz,4H),7.05-7.01(m,2H),6.84(dd,J＝2.0Hz,4.2Hz,2H),2.42(s,3H),1.32(s,12H).
Synthesis of Compound 4:
the synthesis procedure was similar to compound 2, and the crude product was isolated by column chromatography using petroleum ether as eluent to give 7.74g of a white solid with 80% yield.1H NMR(400MHz,CDCl3)δ7.78(d,J＝8.0Hz,1H),7.45(dd,J＝1.6Hz,7.6Hz,2H),7.22(d,J＝4.0Hz,1H),7.05(dd,J＝2.4Hz,8.3Hz,1H),7.00-6.91(m,4H),6.27(dd,J＝1.1Hz,8.0Hz,2H),2.47(s,3H),1.68(s,6H).
Synthesis of compound M4:
the synthesis procedure was similar to compound M2 and the crude product was isolated by column chromatography using petroleum ether dichloromethane (V: V ═ 10:1) as eluent to give 6.27g of a white solid in 79% yield.1H NMR(400MHz,CDCl3)δ8.00(d,J＝8.0Hz,1H),7.44(dd,J＝1.7Hz,7.5Hz,2H),7.14(d,J＝8.0Hz,2H),6.96-6.88(m,4H),6.27(dd,J＝1.4Hz,7.9Hz,2H),2.60(s,3H),1.68(s,6H),1.40(s,12H).
Synthesis of the Compound TPA-BPSP:
to a 100mL single-neck flask were added compound M1(1.25g,2.42mmol), triphenylamine 4-borate (2.10g,7.26mmol), tetrakis (triphenylphosphine) palladium (190mg,0.121mmol), anhydrous potassium carbonate (1.67g,12.1mmol), 5mL deionized water, and 30mL tetrahydrofuran in that order, and the mixture was stirred at 120 ℃ for 24h under nitrogen. After the reaction solution is cooled to room temperature, dichloromethane (3X 30mL) is extracted, and an organic layer is sequentially washed with water (50mL), dried, filtered and distilled under reduced pressure to remove the solvent; the crude product was isolated by column chromatography using petroleum ether and dichloromethane (V: V ═ 1:1) as eluent to give 880mg of a green solid in 43% yield.1H NMR(300MHz,CDCl3)δ8.30(s,2H),7.50-7.47(m,2H),7.40-7.39(m,1H),7.38-7.30(m,15H),7.19-7.15(m,8H),7.12-7.07(m,4H),6.94(s,8H).13C NMR(125MHz,CDCl3)δ148.22,147.50,143.57,141.32,140.00,133.36,133.17,131.15,129.91,129.57,128.69,128.14,124.86,123.58,122.17.MALDI-MS(m/z)of C54H40N2O4S2 for[M]+:calcd.845.04；found,844.24.
Synthesis of the Compound MTPA-BPSP:
the synthetic procedure is similar to that of the compound TPA-BPSB, and the crude product isThe product was separated by column chromatography using petroleum ether and dichloromethane (V: V ═ 1:1) as eluent to give 600mg of yellow solid in 35% yield.1H NMR(400MHz,CDCl3)δ8.29(s,2H),7.51(t,J＝8.0Hz,2H),7.38-7.32(m,16H),7.19(d,J＝8.0Hz,8H),7.09(t,J＝8.0Hz,4H),6.95(d,J＝8.0Hz,1H),6.8(dd,J＝2.0Hz,8.3Hz,1H),6.82(d,J＝8.0Hz,2H),6.77(d,J＝8.0Hz,2H),1.52(s,3H),1.41(s,3H).13C NMR(75MHz,CDCl3)δ148.91,144.16,144.29,141.45,140.31,140.15,138.52,134.05,133.82,132.62,132.15,129.94,129.20,128.92,125.06,123.69,120.75,20.59.MALDI-MS(m/z)of C56H44N2O4S2 for calcd:873.09；found:872.72.
Synthesis of the Compound DMAc-BPSP:
to a 50mL single neck flask were added compound M1(627mg,1.22mmol), compound M2(1.25g,3.04mmol), tetrakis (triphenylphosphine) palladium (84.0mg, 72.9. mu. mol), anhydrous potassium carbonate (839mg,6.08mmol), 3mL deionized water, and 20mL tetrahydrofuran in that order, and the mixture was stirred at 120 ℃ for 24h under nitrogen. When the reaction solution is cooled to room temperature, extracting dichloromethane (3X 30mL), and sequentially washing an organic layer with water (30mL), drying, filtering and distilling under reduced pressure to remove the solvent; the crude product was separated by column chromatography using petroleum ether and dichloromethane (V: V ═ 1.5:1) as eluent to give 400mg of a pale yellow solid in 36% yield.1H NMR(400MHz,CDCl3)δ8.52(s,2H),7.57-7.49(m,10H),7.42-7.38(m,8H),7.30(d,J＝8.0Hz,4H),7.15-7.10(m,4H),7.03-7.00(m,4H),6.42-6.40(m,4H),1.74(s,12H).13C NMR(125MHz,CDCl3)δ143.84,142.11,141.61,141.16,141.06,136.51,134.09,133.71,133.07,131.16,130.70,129.36,128.38,126.74,125.81,121.32,114.46,36.44,31.58.MALDI-MS(m/z)of C60H48N2O4S2 for calcd:925.16；found:925.26.
Synthesis of the compound MDMAc-BPSP:
the synthesis procedure was the same as for the compound DMAc-BPSB, the crude product was purified by using petroleum ether: column chromatography with dichloromethane (V: V ═ 1.5:1) as eluent gave 700mg of a white solid in 38% yield.1H NMR(400MHz,CDCl3)δ8.48(s,2H),7.57(t,J＝8.0Hz,2H),7.54-7.49(m,8H),7.43-7.39(m,4H),7.35(d,J＝8.0Hz,1H),7.21-7.12(m,9H),7.02(t,J＝8.0Hz,4H),6.51(dd,J＝1.8Hz,8.2Hz,4H),1.76(s,3H),1.75(s,12H),1.66(s,3H).13C NMR(75MHz,CDCl3)δ144.11,142.32,141.29,141.11,140.60,140.07,139.94,135.77,134.40,133.75,132.82,130.58,129.47,128.87,128.35,126.85,125.94,121.24,114.48,36.48,31.91,20.50.MALDI-MS(m/z)of C62H52N2O4S2 for calcd:953.22；[M-CH3]+found,937.51.
Example 2
Under nitrogen atmosphere, we tested the thermal stability of TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB with the thermogravimetric curves shown in FIG. 1. As shown in the figure, the decomposition temperatures (T) at 5% weight loss on heating of the compounds TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB are shownd) 487 deg.C, 421 deg.C, 424 deg.C and 430 deg.C, respectively. The compound has better thermal stability.
Example 3
To investigate the photophysical properties of the compounds, solutions and solid films were studied by steady-state, transient fluorescence spectroscopy. As shown in FIG. 2, all compounds absorbed in the toluene solution at 250-500 nm. Wherein short wavelength (<350nm) is attributed to intramolecular pi-pi*Transition, and the absorption between 350-450nm is due to intramolecular charge transfer transition (ICT). Diphenylamine-substituted TPA-BPSP and MTPA-BPSP have stronger ICT transition absorption peaks compared to acridine substitution, which is due to the more distinct HOMO-LUMO electron cloud separation of DMAc-BPSP and MDMAc-BPSP. In the toluene solution, the maximum emission peaks of the compounds TPA-BPSP, DMAc-BPSP, MTPA-BPSP, MDMAc-BPSP were 517nm, 543nm, 527nm and 544nm, respectively (FIG. 3). This shows that the light-emitting range of the material can be effectively adjusted by changing the donor unit and introducing the methyl unit.
To validate the TADF properties of the compounds, we tested the decay lifetime of PMMA films (5% doped) under argon atmosphere. As shown in fig. 4, all compounds were significantly second-order exponential decays in solution, with nanosecond transient lifetimes and microsecond delay lifetimes, respectively. The delayed lifetimes of the compounds TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB in the doped films were 24.2, 12.3, 13.5 and 8.6. mu.s, respectively, confirming that all four target molecules were TADF molecules.
The compounds TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP were further tested for fluorescence quantum efficiency (PLQY) in toluene solution under argon and air atmosphere, respectively. Wherein PLQY of TPA-BPSP, DMAc-BPSP, MTPA-BPSP and MDMAc-BPSP under argon atmosphere is 88, 11, 58 and 1 percent respectively; while in air, PLQY drops sharply to 74, 3, 42, and 1%. This is because triplet excitons of the compound are quenched by triplet oxygen in the air, and the fluorescence quantum efficiency is drastically reduced, confirming that the light emission of the compound is a component of the triplet excitons. Meanwhile, researches show that the introduction of methyl into the molecule causes the PLQY of the molecule to be sharply reduced, because the introduction of the methyl causes the HOMO and LUMO energy levels of the molecule to have smaller overlap, so that the molecule has lower oscillator strength and obtains lower PLQY.
In order to calculate the energy gap difference between the singlet and triplet energy levels of the compound, the fluorescence spectrum and the phosphorescence spectrum of the compound in an oxygen-free toluene solution at 77K were respectively tested. Calculating delta E of the compounds TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB by using the formula E ═ 1240/lambda from the initial peak positions of the low-temperature fluorescence spectrum and the phosphorescence spectrumST0.18, 0.02, 0.07 and 0.01eV, respectively. Obviously, the introduction of methyl units into the molecule can effectively reduce the Delta E of the moleculeSTIncreasing its reverse intersystem crossing rate.
Example 4
All compounds show a mechanically discolored luminescent property under applied external conditions (e.g. milling and fumigation). The maximum occurrence of peaks for the original samples of TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB was 484,521,506 and 510nm, respectively. After pestle grinding in a mortar, the emission spectrum showed a significant red shift with emission peaks at 530(TPA-BPSB),546(DMAc-BPSB),535(MTPA-BPSB) and 560nm (MDMAc-BPSB). After subsequent fumigation with dichloromethane vapor for 15 minutes, the emission color of DMAc-BPSB and MDMAc-BPSB can be reversibly changed back to 527nm and 508nm, which is consistent with the emission spectra in the original state. Although the compounds TPA-BPSB and MTPA-BPSB show a blue shift in the spectra after treatment with methylene chloride vapor, there is a red-shifted emission of about 18nm compared to the original state. Furthermore, the color change between the gas phase and the ground sample is reversible for all compounds.
Example 5
The HOMO and LUMO energy levels of the pure films of four compounds were tested by cyclic voltammetry, and all compounds exhibited only irreversible oxidation potentials in the range of 0V to 2.0V, 1.04V (TPA-BPSB), 1.03V (DMAc-BPSP), 1.06V (MTPA-BPSP), 1.0V (MDMAc-BPSP), respectively. By the formula
The HOMO energy levels of the molecules TPA-BPSB, DMAc-BPSB, MTPA-BPSB and MDMAc-BPSB are calculated to be-5.44, -5.37, -5.41 and-5.33 eV respectively. Acridine-substituted compounds exhibit a higher HOMO energy level than diphenylamine-substituted compounds, mainly due to the fact that acridine has a stronger electron-donating ability. Likewise, the introduction of methyl groups may also slightly raise the HOMO level of the polymer, possibly due to the electron donating ability of the methyl group. Further, by using the optical band gap and the HOMO level, the LUMO levels of the four compounds were calculated to be-2.71, -2.43, -2.55 and-2.21 eV, respectively.
Example 6
In view of higher fluorescence quantum efficiency and good solubility, compounds TPA-BPSP and MTPA-BPSP are selected as luminescent dopants, a device is prepared by a solution processing method, and the relationship between the molecular structure and the device performance is researched. The optimal device structure is ITO/PEDOT: PSS (40nm)/CZAcSF: emitter (x wt%, 50nm)/DEPEO (9nm)/Tmpypb (40nm)/CsF (1.2nm)/Al (120nm), wherein ITO glass is used as an anode, PEDOT: PSS is used as a hole injection layer, CZAcSF is used as a main body material, and DPEPO and TmpyPB are respectively used as a hole blocking layer and an electron transport layer.
As can be seen in the inset of fig. 5, the doping concentration increased from 4% to 10%, and the electroluminescence spectrum of the compound TPA-BPSP slightly red-shifted, probably because the intermolecular interaction increased with the increase in doping concentration, resulting in a red-shift of the spectrum.The CIE coordinates of the devices at doping concentrations of 4%, 7%, and 10% were (0.28,0.47), (0.30,0.49), and (0.31,0.51), respectively. The devices prepared had the optimum performance when the TPA-BPSP doping concentration was 4%, where the maximum luminance was 877.8cd m-2Maximum current efficiency CE of 20.8cd a-1And the maximum external quantum efficiency EQE is 7.27% (fig. 5 and 6). As the doping concentration increases from 4% to 10%, the device efficiency decreases gradually, which is caused by quenching due to strong intermolecular interactions at high doping concentrations.
As can be seen from the inset in FIG. 6, the compound MTPA-BPSP red-shifts the electroluminescence peak from 520nm to 528nm with increasing doping concentration. The CIE coordinates of the MTPA-BPSP based devices at doping concentrations of 4%, 7% and 10% were (0.28,0.48), (0.29,0.50) and (0.28,0.51), respectively. The device exhibited optimal performance when the doping concentration of the compound MTPA-BPSP was 7%, where the maximum luminance, the maximum current efficiency and the maximum external quantum efficiency were 1239cd m-2,53.28cd A-1And 20.5% (fig. 7 and 8). To our knowledge, this is the highest reported electroluminescent device based on a TADF material containing BPSP units prepared by a solution method.
Claims (2)
1. A 'cross' type thermal activity delay fluorescent material is characterized by having a structure of formula 1-formula 6:
2. use of a thermally active delayed fluorescence material according to claim 1, characterized in that: the compound is used as a dopant material of a luminescent layer for a solution processing type organic electroluminescent device, and the maximum external quantum efficiency is as high as 20.5 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506264.7A CN110183361B (en) | 2019-06-12 | 2019-06-12 | Construction and application of cross-shaped thermal activity delay fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506264.7A CN110183361B (en) | 2019-06-12 | 2019-06-12 | Construction and application of cross-shaped thermal activity delay fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110183361A CN110183361A (en) | 2019-08-30 |
| CN110183361B true CN110183361B (en) | 2021-01-29 |
Family
ID=67721610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910506264.7A Active CN110183361B (en) | 2019-06-12 | 2019-06-12 | Construction and application of cross-shaped thermal activity delay fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183361B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620817B (en) * | 2020-06-04 | 2022-09-27 | 常州大学 | Novel blue thermal activity delayed fluorescent material and application thereof |
| CN113683555B (en) * | 2021-08-06 | 2024-01-23 | 常州大学 | D based on biphenyl derivative receptor unit 2 A-type purple light organic luminescent material and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014106987A1 (en) * | 2014-02-14 | 2015-08-20 | Hartmut Yersin | Organic TADF molecules with steric hindrance at the donor and acceptor for opto-electronic devices |
| CN106328816B (en) * | 2015-06-16 | 2018-11-13 | 昆山国显光电有限公司 | A kind of organic electroluminescence device and preparation method thereof |
| CN107056627A (en) * | 2017-04-14 | 2017-08-18 | 南京邮电大学 | A kind of organic semiconductor laser material and preparation method and application |
-
2019
- 2019-06-12 CN CN201910506264.7A patent/CN110183361B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| A donor-acceptor cruciform π-system:high contrast mechanichromic properties and multicolour electrochromic behavior;Sun J.等;《Journal of Materials Chemistry C》;20141231;第2卷(第27期);第5365-5371页 * |
| Aggregation-induced emission in the crystals of 9,10-distyrylanthracene derivatives:the essential role of restricted intramolecular torion;He J.T.等;《The Journal of Physical Chemistry C》;20091231;第113卷;第9892-9899页 * |
| Piezofluorochromism of an aggregation-induced emission compound derived from tetraphenylethylene;Zhang X.Q. 等;《Chemistry-An Asian Journal》;20111231;第808-811页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110183361A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110862381B (en) | Organic electroluminescent compound and preparation method and application thereof | |
| KR101105619B1 (en) | Mixtures of organic emissive semiconductors and matrix materials, their use and electronic components comprising said materials | |
| KR101802526B1 (en) | Materials for organic electroluminescence devices | |
| EP1499624B1 (en) | Electroluminescent materials | |
| CN103958485A (en) | Spirobifluorene compounds for light emitting devices | |
| KR101395080B1 (en) | Novel organic compound for organic electroluminescent device and organic electroluminescent device comprising the same | |
| Han et al. | 1.42-fold enhancement of blue OLED device performance by simply changing alkyl groups on the acridine ring | |
| Park et al. | Synthesis, characterization of the phenylquinoline-based on iridium (III) complexes for solution processable phosphorescent organic light-emitting diodes | |
| KR101764911B1 (en) | Organic electroluminescent compound, ink composition, organic electroluminescent device and electric apparatus | |
| JP6810920B2 (en) | Hole transport compounds and compositions | |
| CN111620817B (en) | Novel blue thermal activity delayed fluorescent material and application thereof | |
| CN109369652B (en) | Blue light thermal activation delayed fluorescent material and application thereof | |
| CN113773349A (en) | Organic electrophosphorescent luminescent material and application thereof in OLED (organic light emitting diode) device | |
| Wang et al. | Purine-based thermally activated delayed fluorescence emitters for efficient organic light-emitting diodes | |
| CN110183361B (en) | Construction and application of cross-shaped thermal activity delay fluorescent material | |
| Huang et al. | Construction of deep-blue AIE luminogens with TPE and oxadiazole units | |
| KR101968353B1 (en) | 1, 2, 4, 5-substituted phenyl derivative, production method for same, and organic electroluminescent element | |
| Ding et al. | Novel spiro-based host materials for application in blue and white phosphorescent organic light-emitting diodes | |
| CN116156980A (en) | Organic electroluminescent device and application thereof | |
| CN107236006B (en) | Red light metal complex and organic electroluminescent device thereof | |
| CN113861206B (en) | Blue electroluminescent material and synthesis method and application thereof | |
| CN111153892B (en) | Novel D-A type TADF material, preparation method and application thereof | |
| CN112062765B (en) | Organic photoelectric luminescent compound and preparation method thereof | |
| CN113698396B (en) | Thermal activation delay fluorescent material and application thereof | |
| CN110655504B (en) | Compound with dibenzosuberene as core and application thereof in organic electroluminescent device |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |