CN112047922A - Benzophenone and benzothiophene-based luminescent material and preparation method and application thereof - Google Patents
Benzophenone and benzothiophene-based luminescent material and preparation method and application thereof Download PDFInfo
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- CN112047922A CN112047922A CN202010819710.2A CN202010819710A CN112047922A CN 112047922 A CN112047922 A CN 112047922A CN 202010819710 A CN202010819710 A CN 202010819710A CN 112047922 A CN112047922 A CN 112047922A
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- luminescent material
- benzophenone
- benzothiophene
- dibenzothiophene
- palladium catalyst
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- 239000000463 material Substances 0.000 title claims abstract description 70
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000012965 benzophenone Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 14
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 235000011056 potassium acetate Nutrition 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- JESBGFNZNSEZMR-UHFFFAOYSA-N 1-bromodibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C=CC=C2Br JESBGFNZNSEZMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- IJICRIUYZZESMW-UHFFFAOYSA-N 2-bromodibenzothiophene Chemical compound C1=CC=C2C3=CC(Br)=CC=C3SC2=C1 IJICRIUYZZESMW-UHFFFAOYSA-N 0.000 claims description 4
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- SNRCKKQHDUIRIY-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloromethane;dichloropalladium;iron(2+) Chemical group [Fe+2].ClCCl.Cl[Pd]Cl.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.C1=C[CH-]C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 SNRCKKQHDUIRIY-UHFFFAOYSA-L 0.000 claims description 3
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 abstract description 16
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007725 thermal activation Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical group [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 7
- 230000007704 transition Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- XTJQPJAUFNYHRW-UHFFFAOYSA-N 2-(1,4-dioxan-2-yl)ethanol;hydrate Chemical compound O.OCCC1COCCO1 XTJQPJAUFNYHRW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 pinacol diboron ester Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- 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
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- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- 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
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- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a luminescent material based on benzophenone and benzothiophene, and a preparation method and application thereof. The structural formula of the luminescent material is shown as a formula (I), and the molecular formula of the luminescent material is C25H16And an OS. The luminescent material provided by the invention has a donor-acceptor structure, wherein a benzophenone unit is used as an electron acceptor, dibenzothiophene is used as an electron donor, the luminescent material has the characteristics of room-temperature phosphorescence and thermal activation delayed fluorescence dual emission, and the thermal activation delayed fluorescence and room-temperature phosphorescence can capture triplet excitons by 100%, so that the internal quantum efficiency of an OLED device can be greatly improved. Meanwhile, the luminescent material is low in cost, simple in preparation method and suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the field of organic luminescent materials, in particular to a luminescent material based on benzophenone and benzothiophene, and a preparation method and application thereof.
Background
The organic light emitting material can be effectively adjusted and changed by simple molecular structure design due to its light emitting characteristics such as light emitting color, intensity and lifetime, thereby attracting much research interest of scientists. The organic light emitting characteristics are embodied in a radiation decay process when excitons in a singlet or triplet excited state transition from an excited state to a ground state, and mainly include a general fluorescent type, a delayed fluorescent type, a room temperature phosphorescent type, and the like.
The room-temperature phosphorescent emission refers to a process in which excitons excited to a singlet state return to a ground state by radiative transition after entering a triplet state through intersystem crossing. The phosphorescence material has strong spin-orbit coupling effect, so that triplet excitons can effectively generate radiative decay, the internal quantum efficiency is high, and the efficiency of the organic electroluminescent device is greatly improved. But the preparation of highly efficient pure organic phosphorescent materials with low toxicity and environmental friendliness is not easy.
Thermally Activated Delayed Fluorescence (TADF) is the lowest excited triplet state (T)1) By endothermic up-conversion of T1The exciton intersystem crossing back to the lowest excited singlet state (S)1) And then from S1Fluorescence generated by radiative transition to the ground state. For TADF molecules, almost 100% conversion of triplet excitons to singlet states has been achieved to become a third generation organic light emitting material following conventional fluorescent and phosphorescent materials.
Currently, most of the high-efficiency thermally activated delayed fluorescence and room temperature phosphorescence materials are complexes formed by noble metal-organic ligand, and although the materials have excellent luminous efficiency, the moisture resistance and stability of the materials are generally poorer than those of pure organic materials, and the cost is higher. And there are only few reports on a luminescent material combining room temperature phosphorescence and TADF emission. The chinese patent application CN 110016335 a discloses a pure organic room temperature phosphorescent material with ether bond, which has simple preparation process, but only has room temperature phosphorescent emission characteristic, not TADF molecule. A series of cyclic micromolecules are prepared from the Hu Ying (the Hu Ying is based on the synthesis of an organic luminescent material of diphenyl sulfide and oxides thereof and the photoelectric properties [ D ] thereof), researches show that the cyclic micromolecules not only have the thermal activation delayed fluorescence property, but also have the room-temperature phosphorescence property under the states of spin-coating pure films and single crystals, but the compounds have complex structures and higher preparation difficulty and have high requirements for industrial large-scale production.
Therefore, it is required to develop a pure organic light emitting material which is easy to synthesize, has a simple structure, and has both room temperature phosphorescence and TADF emission.
Disclosure of Invention
The invention provides a luminescent material based on benzophenone and benzothiophene, aiming at overcoming the defect of complex preparation process in the prior art. The luminescent material has the thermal activation delayed fluorescence property of weak room temperature phosphorescence emission, and can be directly used as a luminescent material for application.
Another object of the present invention is to provide a method for preparing the above mentioned luminescent material based on benzophenone and benzothiophene.
Still another object of the present invention is to provide the use of the above mentioned benzophenone and benzothiophene based luminescent materials.
In order to solve the technical problems, the invention adopts the technical scheme that:
a benzophenone and benzothiophene based luminescent material having the formula (I):
the molecular formula of the luminescent material shown as the formula (I) is C25H16OS。
The luminescent material has a donor-acceptor structure, wherein a benzophenone unit is used as an electron acceptor, and dibenzothiophene is used as an electron donor. Based on the design strategy of an electron donor-acceptor structure, the characteristic can effectively adjust the molecular energy level so as to promote the emission of room-temperature phosphorescence and thermally-activated delayed fluorescence.
The invention also provides a preparation method of the luminescent material, which comprises the following steps:
s1, dissolving 2-bromodibenzothiophene, diboron pinacol ester, acetate and a palladium catalyst in an organic solvent, and performing heating reaction and post-treatment to obtain 2-boronic pinacol ester-dibenzothiophene;
s2, dissolving 2-pinacol borate-dibenzothiophene 4-bromobenzophenone, carbonate and a palladium catalyst in an organic solvent, and performing heating reaction and post-treatment to obtain the luminescent material based on benzophenone and benzothiophene.
Preferably, the acetate is potassium acetate and the carbonate is sodium carbonate.
Preferably, the palladium catalyst is 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex and/or tetrakis (triphenylphosphine) palladium.
Preferably, in step S1, the palladium catalyst is 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex; in step S2, the palladium catalyst is tetrakis (triphenylphosphine) palladium.
Preferably, the organic solvent is an aqueous ethanol solution containing 1, 4-dioxane.
More preferably, the volume ratio of 1, 4-dioxane, ethanol and water in the ethanol aqueous solution containing 1, 4-dioxane is 6: 2: 1.
preferably, the post-treatment comprises extraction, desolventization, purification.
More preferably, the purification is performed using silica gel column chromatography, and the eluent is ethyl acetate and n-hexane.
Preferably, the molar ratio of the bromodibenzothiophene, pinacol bisborate, potassium acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex in the step S1 is 1: 1-2: 1-4: 0.02-0.06.
More preferably, the molar ratio of bromodibenzothiophene, pinacol diborate, potassium acetate, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium dichloromethane complex in step S1 is 1: 3: 0.03.
Preferably, the reaction temperature in the step S1 is 70-110 ℃, and the reaction time is 16-24 h.
More preferably, the temperature of the reaction in step S1 is 90 ℃ and the reaction time is 20 h.
The synthetic route of step S1 is as follows:
specifically, the operation of step S1 may be: a 100mL round bottom flask was charged with 2-bromodibenzothiophene, pinacol diboron, potassium acetate, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium dichloromethane complex and a 1, 4-dioxane-ethanol-water mixture. The reactants are heated to 90 ℃ and reacted for 20h under the protection of nitrogen. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted with dichloromethane and saturated brine 3 times. The organic phase was taken and the dichloromethane was evaporated under reduced pressure to give the crude product. Separating and purifying by silica gel column chromatography with ethyl acetate/n-hexane as eluent to obtain 2-pinacol borate-dibenzothiophene.
Preferably, in step S2, the molar ratio of the 2-pinacol borate-dibenzothiophene, 4-bromobenzophenone, sodium carbonate and tetrakis (triphenylphosphine) palladium is 1-4: 2-6: 1-4: 0.03 to 0.08.
More preferably, the molar ratio of the 2-pinacol borate-dibenzothiophene, 4-bromobenzophenone, sodium carbonate, tetrakis (triphenylphosphine) palladium in step S2 is 2: 3: 2: 0.06.
preferably, the reaction temperature in the step S2 is 60-115 ℃, and the reaction time is 12-20 h.
More preferably, the temperature of the reaction in step S2 is 85 ℃ and the reaction time is 16 h.
The synthetic route of step S2 is as follows:
specifically, the operation of step S2 may be: a100 mL round bottom flask was charged with a mixture of 4-bromobenzophenone, 2-boronic acid pinacol ester-dibenzothiophene, sodium carbonate, tetrakis (triphenylphosphine) palladium and 1, 4-dioxane-ethanol-water. The reactants are heated to 85 ℃ under the protection of nitrogen and reacted for 16 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted with dichloromethane and saturated brine 3 times. The organic phase was taken and the dichloromethane was evaporated under reduced pressure to give the crude product. And separating and purifying by silica gel column chromatography with ethyl acetate/n-hexane as eluent to obtain the benzophenone and benzothiophene based luminescent material.
The invention also protects the application of the luminescent material based on the benzophenone and the benzothiophene in the aspects of anti-counterfeiting marks, luminescent devices or biological imaging.
Compared with the prior art, the invention has the beneficial effects that:
the invention creatively synthesizes a luminescent material based on benzophenone and benzothiophene, and the molecular formula of the luminescent material is C25H16And an OS. The luminescent material has low cost and simple preparation method, and is suitable for industrial large-scale production. Meanwhile, the luminescent material has the characteristics of room-temperature phosphorescence and TADF dual emission, and the TADF and the room-temperature phosphorescence can capture triplet excitons by 100%, so that the internal quantum efficiency of the OLED device can be greatly improved.
Drawings
FIG. 1 is a drawing showing a luminescent material prepared in example 11H MNR diagram.
FIG. 2 is a drawing showing a luminescent material prepared in example 113C MNR diagram.
FIG. 3 shows the temperature-dependent steady-state spectra of the doped thin film of luminescent material prepared in example 1 under the protection of nitrogen, wherein the excitation wavelength is 298nm, and the test temperatures are 77.5, 100.1, 150.0, 199.9, 250.0 and 300.0K, respectively.
FIG. 4 shows normalized temperature-dependent steady-state spectra of the doped thin film of luminescent material prepared in example 1 under the protection of nitrogen, wherein the excitation wavelength is 298nm, and the test temperatures are 77.5K and 300.0K, respectively.
FIG. 5 is a graph of the decay of the fluorescence lifetime under nitrogen protection and different temperature conditions for the doped film of luminescent material prepared in example 1, wherein the excitation wavelength is 298nm, the emission wavelength is 410nm, and the test temperatures are 78.1, 100.0, 150.0, 200.1, 250.0 and 300.0K, respectively.
FIG. 6 is a graph of the phosphorescence lifetime decay of the doped thin film of the luminescent material prepared in example 1 under the protection of nitrogen and different temperature conditions, wherein the excitation wavelength is 298nm, the emission wavelength is 582nm, and the test temperatures are 77.8, 100.1, 150.0, 200.0, 250.0 and 300.0K, respectively.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples are all commercially available;
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
This example provides a benzophenone and benzothiophene based luminescent material with a molecular formula of C25H16OS, of the formula (I):
the preparation method of the luminescent material comprises the following steps:
s1, adding 2-bromodibenzothiophene, pinacol diboron ester, potassium acetate, [1,1 '-bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex and a 1, 4-dioxane-ethanol-water mixed solution into a 100mL round bottom flask, wherein the molar ratio of the bromodibenzothiophene, the pinacol diboron ester, the potassium acetate, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex is 1: 3: 0.03. The reactants are heated to 90 ℃ and reacted for 20h under the protection of nitrogen. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted with dichloromethane and saturated brine 3 times. The organic phase was taken and the dichloromethane was evaporated under reduced pressure to give the crude product. Separating and purifying by silica gel column chromatography with ethyl acetate/n-hexane as eluent to obtain 2-pinacol borate-dibenzothiophene.
The synthetic route of step S1 is as follows:
s2, adding a mixed solution of 4-bromobenzophenone, 2-pinacol borate-dibenzothiophene, sodium carbonate, tetrakis (triphenylphosphine) palladium and 1, 4-dioxane-ethanol-water into a 100mL round-bottom flask, wherein the molar ratio of the 2-pinacol borate-dibenzothiophene, the 4-bromobenzophenone, the sodium carbonate and the tetrakis (triphenylphosphine) palladium is 2: 3: 2: 0.06. the reactants are heated to 85 ℃ under the protection of nitrogen and reacted for 16 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was extracted with dichloromethane and saturated brine 3 times. The organic phase was taken and the dichloromethane was evaporated under reduced pressure to give the crude product. And separating and purifying by silica gel column chromatography with ethyl acetate/n-hexane as eluent to obtain the benzophenone and benzothiophene based luminescent material.
The synthetic route of step S2 is as follows:
example 2
This example provides a benzophenone and benzothiophene based luminescent material, which is prepared by the following method, in contrast to example 1:
in step S1, the molar ratio of bromodibenzothiophene, pinacol diboron, potassium acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex is 1: 0.02; in step S2, the molar ratio of 2-boronic acid pinacol ester-dibenzothiophene, 4-bromobenzophenone, sodium carbonate, and tetrakis (triphenylphosphine) palladium is 1: 2: 1: 0.03.
example 3
This example provides a benzophenone and benzothiophene based luminescent material, which is prepared by the following method, in contrast to example 1:
in step S1, the molar ratio of bromodibenzothiophene, pinacol diboron, potassium acetate and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride dichloromethane complex is 1: 2: 4: 0.06; in step S2, the molar ratio of 2-boronic acid pinacol ester-dibenzothiophene, 4-bromobenzophenone, sodium carbonate, and tetrakis (triphenylphosphine) palladium is 4: 6: 4: 0.08.
example 4
This example provides a benzophenone and benzothiophene based luminescent material, which is prepared by the following method, in contrast to example 1:
in the step S1, under the protection of nitrogen, the reactants are heated to 70 ℃ and reacted for 16 h; in step S2, the reactant is heated to 60 ℃ and reacted for 12h under the protection of nitrogen.
Example 5
This example provides a benzophenone and benzothiophene based luminescent material, which is prepared by the following method, in contrast to example 1:
in the step S1, under the protection of nitrogen, the reactants are heated to 110 ℃ and react for 24 h; in step S2, the reactant is heated to 115 ℃ and reacted for 20h under the protection of nitrogen.
Performance testing
The benzophenone and benzothiophene based luminescent materials prepared in example 1 were selected for performance testing.
The test method is as follows:
and (3) detecting the structure of the compound: using a Bruk 400MHz superconducting nuclear magnetic resonance instrument, wherein a solvent is deuterated DMSO;
and (3) emission spectrum detection: using a steady state/transient state fluorescence spectrometer (FLS980), wherein the excitation wavelength is 298nm, and the test temperatures are 77.5, 100.1, 150.0, 199.9, 250.0 and 300.0K respectively under the protection of nitrogen;
detection of delayed fluorescence lifetime decay: adopting a steady-state/transient fluorescence spectrometer (FLS980), wherein the excitation wavelength is 298nm, the emission wavelength is 410nm, and the test temperatures are respectively 78.1, 100.0, 150.0, 200.1, 250.0 and 300.0K under the protection of nitrogen;
phosphorescence lifetime decay detection: a steady-state/transient fluorescence spectrometer (FLS980) is adopted, the excitation wavelength is 298nm, the emission wavelength is 582nm, and the test temperatures are 77.8, 100.1, 150.0, 200.0, 250.0 and 300.0K respectively under the protection of nitrogen.
The test results were as follows:
the molecular hydrogen spectrum and the molecular carbon spectrum of the benzophenone and benzothiophene-based luminescent material prepared in example 1 are shown in fig. 1 and fig. 2, respectively. It can be seen that:
1h NMR (400MHz, DMSO-d6)8.83(d, J ═ 1.6Hz,1H), 8.60-8.54 (m,1H),8.18(d, J ═ 8.4Hz,1H),8.07(dd, J ═ 8.9,2.5Hz,3H),7.94(dd, J ═ 8.4,1.8Hz,1H),7.90(d, J ═ 8.4Hz,2H), 7.84-7.77 (m,2H),7.72(t, J ═ 7.4Hz,1H),7.58(ddd, J ═ 11.1,9.9,5.8Hz,4H), and the peaks in the molecular hydrogen spectrum can correspond to the target product, one-to-one, and in a reasonable amount;
13c NMR (101MHz, DMSO)195.86(s,1H),144.49(s,1H),139.55(s,1H),139.25(s,1H),137.70(s,1H), 136.47-136.06 (m,4H),135.49(s,1H),133.15(s,3H),130.95(s,5H),130.06(s,5H),129.10(s,5H),127.87(s,2H),127.55(s,5H),126.41(s,3H),125.34(s,2H),124.16(s,3H),123.62(s,3H),122.98(s,3H),120.93(s,3H) the fragment peaks of the molecular carbon spectrum are consistent with the molecular weight of the luminescent material prepared in example 1 and free of hetero peaks, indicating that the molecular weight is determined and the purity is high.
The doped film is prepared by using the luminescent material, and the preparation method comprises the following steps: weighing a certain mass of sample, preparing the sample by using a soluble solvent, and preparing the film by using a spin-coating solvent evaporation method.
The luminescent performance of the luminescent material doped thin film was tested, and the results are shown in fig. 3 and 4. Fig. 3 is a temperature-dependent steady-state spectrum of the luminescent material doped film under nitrogen protection, and fig. 4 is a normalized temperature-dependent steady-state spectrum of the luminescent material doped film under nitrogen protection.
Under low temperature conditions, the maximum emission peak of the film is at 550nm, the peak intensity continuously decreases with increasing temperature until the maximum emission wavelength shifts to 450nm when the temperature reaches 200K, the peak emission intensity conversely increases with increasing temperature from 200K to 250K, and the emission intensity slightly decreases from 250K to 300K due to the increase of non-radiative transitions.
The detection of the delayed fluorescence lifetime decay and the phosphorescence lifetime decay at the characteristic wavelength is performed on the luminescent material doped film, and the test results are shown in fig. 5 and 6. FIG. 5 is a graph of the decay of the lifetime of delayed fluorescence for a film with an excitation wavelength of 298nm, an emission wavelength of 410nm, and test temperatures of 78.1, 100.0, 150.0, 200.1, 250.0, 300.0K, respectively; FIG. 6 is a graph of phosphorescence lifetime decay at an excitation wavelength of 298nm, an emission wavelength of 582nm, and test temperatures of 77.8, 100.1, 150.0, 200.0, 250.0, and 300.0K, respectively.
As shown in fig. 5 and 6, the proportion of the delayed component corresponding to the emission peak at 410nm increases significantly with the increase of temperature from 150K to 300K, indicating that the thermal energy can effectively promote the transition process between the opposite systems, which satisfies the characteristic of thermally activated delayed fluorescence, and it can be seen that the luminescent material prepared in example 1 is a thermally activated delayed fluorescent material. Whereas the intensity of afterglow in the decay curve at 582nm shown in fig. 6 has a rather pronounced tendency to decrease with increasing temperature, since the non-radiative transition rate constant increases with increasing temperature, resulting in a decrease of the decay intensity for long lifetimes, which is characteristic of typical room temperature phosphorescent materials. Therefore, the luminescent material is a thermally activated delayed fluorescence material with room temperature phosphorescent emission, i.e. the luminescent material has both room temperature phosphorescent emission and thermally activated delayed fluorescence.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A luminescent material based on benzophenone and benzothiophene, characterized in that the structural formula of the luminescent material is shown in formula (I):
2. a method for preparing a benzophenone and benzothiophene based luminescent material as claimed in claim 1, characterized in that it comprises the following steps:
s1, dissolving 2-bromodibenzothiophene, diboron pinacol ester, acetate and a palladium catalyst in an organic solvent, and performing heating reaction and post-treatment to obtain 2-boronic pinacol ester-dibenzothiophene;
s2, dissolving 2-pinacol borate-dibenzothiophene, 4-bromobenzophenone, carbonate and a palladium catalyst in an organic solvent, and performing heating reaction and post-treatment to obtain the luminescent material based on benzophenone and benzothiophene.
3. The production method according to claim 2, wherein the palladium catalyst is 1,1' -bis (diphenylphosphino) ferrocene dichloropalladium dichloromethane complex and/or tetrakis (triphenylphosphine) palladium.
4. The method according to claim 2, wherein the molar ratio of the bromodibenzothiophene, pinacol diboron diborate, potassium acetate and palladium catalyst in step S1 is 1: 1-2: 1-4: 0.02-0.06.
5. The method according to claim 2, wherein the heating reaction in step S1 is carried out at a temperature of 70-110 ℃ for 16-24 h.
6. The preparation method according to claim 2, wherein the molar ratio of the 2-pinacol borate-dibenzothiophene, 4-bromobenzophenone, sodium carbonate and palladium catalyst in step S2 is 1 to 4: 2-6: 1-4: 0.03 to 0.08.
7. The method according to claim 2, wherein the heating reaction in step S2 is carried out at a temperature of 60-115 ℃ for 12-20 hours.
8. The method according to claim 2, wherein the organic solvent is an aqueous ethanol solution containing 1, 4-dioxane.
9. The method according to claim 8, wherein the volume ratio of 1, 4-dioxane, ethanol and water in the organic solvent is 6: 2: 1.
10. use of the benzophenone and benzothiophene based luminescent material of claim 1 in anti-counterfeiting marks, light emitting devices or bio-imaging.
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