CN110283209B - Phosphino-oxygen group modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material, and synthesis method and application thereof - Google Patents
Phosphino-oxygen group modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material, and synthesis method and application thereof Download PDFInfo
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- CN110283209B CN110283209B CN201910359637.2A CN201910359637A CN110283209B CN 110283209 B CN110283209 B CN 110283209B CN 201910359637 A CN201910359637 A CN 201910359637A CN 110283209 B CN110283209 B CN 110283209B
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- 239000000463 material Substances 0.000 title claims abstract description 116
- 230000005284 excitation Effects 0.000 title claims abstract description 78
- 230000003111 delayed effect Effects 0.000 title claims abstract description 68
- NRXKEONAFOCNGW-UHFFFAOYSA-N [O]P Chemical group [O]P NRXKEONAFOCNGW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 261
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000012044 organic layer Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 19
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 18
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 18
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001632 sodium acetate Substances 0.000 claims abstract description 18
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 96
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 52
- 239000010410 layer Substances 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000012046 mixed solvent Substances 0.000 claims description 30
- -1 phosphino-oxygen-group-modified bipyridyl phenazine Chemical compound 0.000 claims description 29
- 229910052770 Uranium Inorganic materials 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 238000004440 column chromatography Methods 0.000 claims description 23
- 239000003480 eluent Substances 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- PVWHEXBKSREKSB-UHFFFAOYSA-N 2,9-dibromo-1,10-phenanthroline-5,6-dione Chemical compound C1=C(Br)N=C2C3=NC(Br)=CC=C3C(=O)C(=O)C2=C1 PVWHEXBKSREKSB-UHFFFAOYSA-N 0.000 claims description 17
- IFZAYEPOLKDKNV-UHFFFAOYSA-N 3,8-dibromo-1,10-phenanthroline-5,6-dione Chemical compound BrC1=CN=C2C3=NC=C(Br)C=C3C(=O)C(=O)C2=C1 IFZAYEPOLKDKNV-UHFFFAOYSA-N 0.000 claims description 17
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 17
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- BKLOILHQTLWRIC-UHFFFAOYSA-N NC(C(N)=C(C=C1)P(C2=CC=CC=C2)(C2=CC=CC=C2)=O)=C1C(C=C1)=CC=C1N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound NC(C(N)=C(C=C1)P(C2=CC=CC=C2)(C2=CC=CC=C2)=O)=C1C(C=C1)=CC=C1N(C1=CC=CC=C1)C1=CC=CC=C1 BKLOILHQTLWRIC-UHFFFAOYSA-N 0.000 claims description 8
- XTGLVZYRYZZUAS-UHFFFAOYSA-N NC(C(N)=C1)=CC(C(C=C2)=CC=C2N(C2=CC=CC=C2)C2=CC=CC=C2)=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)=O Chemical compound NC(C(N)=C1)=CC(C(C=C2)=CC=C2N(C2=CC=CC=C2)C2=CC=CC=C2)=C1P(C1=CC=CC=C1)(C1=CC=CC=C1)=O XTGLVZYRYZZUAS-UHFFFAOYSA-N 0.000 claims description 8
- KTBQAIZSBMIAPK-UHFFFAOYSA-N NC(C=C1)=CC=C1C(C(C(C=C1)=CC=C1N)=C1)=CC(N)=C1N Chemical compound NC(C=C1)=CC=C1C(C(C(C=C1)=CC=C1N)=C1)=CC(N)=C1N KTBQAIZSBMIAPK-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- LPZFVLLSNKXUCF-UHFFFAOYSA-N NC(C=C1)=CC=C1C1=CC=C(C(C=C2)=CC=C2N)C(N)=C1N Chemical compound NC(C=C1)=CC=C1C1=CC=C(C(C=C2)=CC=C2N)C(N)=C1N LPZFVLLSNKXUCF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims 6
- 230000000171 quenching effect Effects 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 3
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- 238000002189 fluorescence spectrum Methods 0.000 description 48
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 17
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 16
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 9
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ONAJRJLKMDMICA-UHFFFAOYSA-N C1=CC=NC(=C1)C2=C(C=CC(=N2)Br)Br Chemical group C1=CC=NC(=C1)C2=C(C=CC(=N2)Br)Br ONAJRJLKMDMICA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 101100327050 Caenorhabditis elegans cbp-1 gene Proteins 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
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- 238000005401 electroluminescence Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical group C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
- C07F9/65616—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings containing the ring system having three or more than three double bonds between ring members or between ring members and non-ring members, e.g. purine or analogs
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Abstract
A phosphino-oxygen group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material, a synthetic method and application thereof, relating to a thermal excitation delayed fluorescence material, a synthetic method and application thereof. The invention aims to solve the problems of concentration quenching and low efficiency and fast attenuation of an electroluminescent device caused by large molecular polarity of the conventional red/near infrared TADF material. The structural formula is as follows:
the synthesis method comprises the following steps: firstly, preparing an intermediate; and secondly, mixing the intermediate, palladium acetate, sodium acetate, diphenylphosphine and N, N-dimethylformamide, reacting for 48 hours at 150 ℃, oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying to obtain the phosphino-oxygen group modified bipyridyl-phenazinyl red light/near infrared thermal excitation delay fluorescent material. The material provided by the invention can obviously improve the efficiency of the electroluminescent device, reduce the quenching effect and enhance the efficiency stability of the electroluminescent device. The invention belongs to the field of preparation of fluorescent materials.
Description
Technical Field
The invention relates to a thermal excitation delayed fluorescence material, a synthetic method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have been drawing attention due to their outstanding advantages of Light weight, flexibility, low power consumption, and low cost, and have become the leading people in the field of new generation of flat panel display technology and illumination. In the light emitting layer of the organic light emitting diode, excitons formed by recombination of holes and electrons injected from the anode and the cathode, respectively, are divided into excited singlet excitons and excited triplet excitons with a ratio of the number of the excitons being 1: 3. Singlet excitons radiate back to the ground state to emit fluorescence, while triplet excitons are spin-forbidden, and cannot undergo the process of radiating back from the triplet state to the ground state, and are mostly lost in the form of heat energy. So that the first generation OLEDs, which were originally based on fluorescent materials, can only utilize 25% of singlet excitons, with IQE of only 25%. Later, in order to utilize 75% of triplet excitons generated by recombination, researchers have introduced transition metal phosphine light materials into the light emitting layer of organic light emitting diodes, in such molecules, intersystem crossing (ISC) processes are accelerated due to heavy atom effects, triplet excitons may undergo a process of falling from an excited state to a ground state, both singlet and triplet excitons may be captured by the light emitting material due to the spin-orbit coupling effect of heavy metals, and radiation is attenuated back to the ground state, thereby achieving effective utilization of all excitons, theoretically up to 100% IQE. In recent years, the advent of Thermally Activated Delayed Fluorescence (TADF) materials has provided researchers with new design considerations. Under the action of an external voltage electric field force, electrons and holes respectively reach the light-emitting layer through the electron and hole transport layers, are combined to form 25% of singlet state excitons and 75% of triplet state excitons under the action of coulomb force, and have the lowest singlet excited state-triplet excited state energy range difference (delta E)ST) Smaller (<0.5eV), the triplet excitons may form singlet excitons through trans-intersystem crossing (RISC) to singlet states with the support of external thermal energy, and then the singlet excitons S1The fluorescence generated by radiative transition is the Delayed Fluorescence (DF), so that the theoretical maximum internal quantum efficiency of the device can reach 100 percent. It can break through the limit of only 25% theoretical internal quantum efficiency of traditional fluorescence OLEDs, and realize 100% internal quantum efficiency. Compared with the traditional phosphine-based OLEDs, the technologyThe method does not need to use a heavy metal doped phosphine optical material, so that on one hand, the use of expensive heavy metal can be avoided, and the production cost of the device is reduced. Therefore, designing and synthesizing the efficient red/near infrared TADF material is a significant scientific research subject.
In recent years, the aromatic phosphine oxide material has attracted great interest due to its outstanding advantages, and is used for designing and constructing efficient electroluminescent host materials, luminescent materials and the like. The phosphine oxide (P ═ O) group connects the aromatic groups through C-P saturated bonds, so that the conjugated extension can be effectively blocked, and the emission wavelength of the material is not influenced; meanwhile, the P ═ O group has the function of polarizing molecules, so that the electron injection and transmission capability of the material can be improved; in addition, the diphenyl phosphine oxide group also has larger steric hindrance effect, and can effectively inhibit the interaction between molecules. Therefore, the introduction of phosphine-oxygen groups into the donor-acceptor structure can adjust the molecular configuration, the electrical property and the like of the material on the premise of not influencing the emission wavelength of the material, and is expected to realize the efficient red/near infrared TADF material.
Disclosure of Invention
The invention aims to solve the technical problems of concentration quenching, low efficiency of an electroluminescent device and quick attenuation of the traditional red/near infrared TADF material due to large molecular polarity, and provides a phosphino-oxygen group modified bipyridyl-phenazinyl red/near infrared thermal excitation delay fluorescent material, a synthesis method and application thereof.
The phosphine oxide group modified bipyridyl phenazine based red/near infrared thermal excitation delay fluorescent material has the following structural formula:
wherein X is hydrogen or
Y is hydrogen,
Z is hydrogen,
W is hydrogen or
M is hydrogen or
V is hydrogen or
N is hydrogen or
U is hydrogen or
When W, Y, Z, M, V is hydrogen, X is
N, U is
When, its structural formula is:
when W, Z, M, V is hydrogen, X, Y is
N, U is
When, its structural formula is:
when X, Y, Z, M, V is hydrogen, W is
N, U is
When, its structural formula is:
when X, Y, M, V is hydrogen, W, Z is
N, U is
When, its structural formula is:
when W, Z, M, V is hydrogen, X is
Y, N, U is
When, its structural formula is:
when X, Y, M, V is hydrogen, W is
Z, N, U is
When, its structural formula is:
when W, Y, Z, N, U is hydrogen, X is
M, V is
When, its structural formula is:
when W, Z, N, U is hydrogen, X, Y is
M, V is
When, its structural formula is:
when X, Y, Z, N, U is hydrogen, W is
M, V is
When, its structural formula is:
when X, Y, N, U is hydrogen, W, Z is
M, V is
When, its structural formula is:
when W, Z, M, V is hydrogen, X is
Y, N, U is
When, its structural formula is:
when X, Y, N, U is hydrogen, W is
Z, M, V is
When, its structural formula is:
the synthesis method of the phosphino-oxygen-group-modified bipyridyl phenazinyl red/near-infrared thermal excitation delayed fluorescence material comprises the following steps:
firstly, mixing 0.8-1.2 mmol of 2, 9-dibromo-phenanthroline-5, 6-dione or 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of reaction precursor and 5-10 ml of ethanol, reacting at 80 ℃ for 48 hours, extracting with water and dichloromethane, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of dichloromethane to ethyl acetate is 5: 1-2: 1) as an eluent to obtain an intermediate;
secondly, taking 1mmol of the intermediate synthesized in the step one, 0.05mmol of palladium acetate, 1-10 mmol of sodium acetate, 1mmol of diphenylphosphine and 5-10 ml of N, N-dimethylformamide, mixing, reacting at 150 ℃ for 48H, and adding 5mmol of H2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing an organic solvent, performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate (gradient elution is performed between dichloromethane and ethyl acetate in a volume ratio of 2: 1-1: 5) as an eluent to obtain the phosphino group modified bipyridyl-phenazine-based red/near-infrared thermal excitation delayed fluorescent material.
In the first step, the reaction precursor is N4', N4' -diphenyl- [1,1' -biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1' -biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4' -tetraphenyl [1,1 ': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1 "-terphenyl ] -2', 3', 4, 4" -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide, (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide, N4', N4' -diphenyl- [1,1' -biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1' -biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1' -terphenyl ] -2', 3', 4,4' -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide or (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide.
The group provided by the reaction precursor in the step one is
In step two, the group provided by the intermediate is
The phosphino-oxygen group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material is used for an organic electroluminescent device.
The phosphine oxide group modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material is applied as follows:
the method comprises the steps of firstly manufacturing a conducting layer, then evaporating a hole transport layer material on the conducting layer, evaporating a doping body luminescent layer of a phosphino-oxygen group modified bipyridyl-phenazine-based red light/near infrared thermal excitation delay fluorescent material and a main material on the hole transport layer, evaporating an electron transport layer material on the luminescent layer, and finally evaporating a second conducting layer.
The doping body is doped with a red light/near infrared thermal excitation delay fluorescent material modified by CBP and phosphine oxide groups.
The phosphino-oxygen group modified bipyridyl-phenazine-based red/near-infrared thermal excitation delayed fluorescence material provided by the invention takes triphenylamine as a donor and a bipyridyl-phenazine ring as an acceptor, and a donor-acceptor structure with red/near-infrared emission is constructed. And then, a diphenyl phosphine-oxygen group is introduced as a second acceptor to finely adjust the photoelectric characteristics of the material, the polarization effect of the phosphine-oxygen group obviously enhances the electron injection and transmission capability of the material, and in addition, the steric effect of the phosphine-oxygen group effectively inhibits the quenching effect caused by the interaction between molecules. Finally obtaining the high-efficiency bipyridyl phenazine based red/near infrared thermal excitation delay fluorescent material modified by phosphine oxide groups.
The application of the phosphino-oxygen group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material in an electroluminescent device has the following advantages:
1. the thermal excitation delay fluorescent material can emit light by utilizing singlet excitons and triplet excitons at the same time, so that the efficiency of the electroluminescent device is remarkably improved;
2. the larger steric hindrance effect of the material molecules can effectively inhibit the interaction between molecules, reduce the quenching effect and enhance the efficiency stability of the electroluminescent device.
3. The polarization of phosphine-oxygen group can improve the electron injection and transmission capability of the material and reduce the driving voltage of the electroluminescent device.
Drawings
FIG. 1 is a UV fluorescence spectrum of Compound 1 synthesized in experiment one, wherein ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 2 is a thermogravimetric analysis of experiment one synthesized Compound 1;
FIG. 3 is a UV fluorescence spectrum of Compound 2 synthesized in experiment two, wherein ■ represents a UV spectrum in methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 4 is a thermogravimetric analysis spectrum of Compound 2 synthesized in experiment two;
FIG. 5 is a UV fluorescence spectrum of Compound 3 synthesized in experiment three, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 6 is a thermogravimetric analysis spectrum of Compound 3 synthesized in experiment three;
FIG. 7 is a UV fluorescence spectrum of Compound 4 synthesized in experiment IV, in which ■ represents a UV spectrum of a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum of a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 8 is a thermogravimetric analysis spectrum of Compound 4 synthesized in experiment four;
FIG. 9 is a UV fluorescence spectrum of Compound 5 synthesized in experiment five, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 10 is a thermogravimetric analysis spectrum of Compound 5 synthesized in experiment five;
FIG. 11 is a UV fluorescence spectrum of Compound No. 6 synthesized in experiment six, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 12 is a thermogravimetric analysis spectrum of Compound 6 synthesized in experiment six;
FIG. 13 is a UV fluorescence spectrum of Compound 7 synthesized in experiment seven, wherein ■ represents a UV spectrum in methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 14 is a thermogravimetric analysis spectrum of Compound 7 synthesized in experiment seven;
FIG. 15 is a UV fluorescence spectrum of Compound 8 synthesized in Experimental eight, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 16 is a thermogravimetric analysis spectrum of Compound 8 synthesized in Experimental eight;
FIG. 17 is a UV fluorescence spectrum of Compound 9 synthesized in experiment three, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 18 is a thermogravimetric analysis spectrum of Compound 9 synthesized in experiment three;
FIG. 19 is a UV fluorescence spectrum of Compound 10 synthesized in experiment IV, in which ■ represents a UV spectrum of a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum of a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 20 is a thermogravimetric analysis spectrum of Compound 10 synthesized in experiment four;
FIG. 21 is a UV fluorescence spectrum of Compound No. 11 synthesized in experiment five, in which ■ represents a UV spectrum of a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum of a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 22 is a thermogravimetric analysis spectrum of Compound 11 synthesized in experiment five;
FIG. 23 is a UV fluorescence spectrum of Compound 12 synthesized in experiment six, in which ■ represents a UV spectrum in a methylene chloride solvent, ● represents a UV spectrum of a thin film, □ represents a fluorescence spectrum in a methylene chloride solvent, and O represents a fluorescence spectrum of a thin film;
FIG. 24 is a thermogravimetric analysis spectrum of Compound 12 synthesized in experiment six;
fig. 25 is a voltage-current density plot for a doped, electroluminescent, red TADF device prepared with compound 1;
fig. 26 is a voltage-luminance graph of a doped electroluminescent red TADF device prepared with compound 1;
fig. 27 is a current density-current efficiency curve for a doped, electroluminescent, red TADF device prepared with compound 1;
fig. 28 is a current density-power efficiency plot for a doped, electroluminescent, red TADF device prepared with compound 1;
fig. 29 is a current density-external quantum efficiency curve for a doped, electroluminescent, TADF device prepared with compound 1;
fig. 30 is an electroluminescence spectrum of a doped type electroluminescent red TADF device prepared with compound 1.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the structural formula of the phosphino-oxygen group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material is as follows:
wherein X is hydrogen or
Y is hydrogen,
Z is hydrogen,
W is hydrogen or
M is hydrogen or
V is hydrogen or
N is hydrogen or
U is hydrogen or
When W, Y, Z, M, V is hydrogen, X is
N, U is
When, its structural formula is:
when W, Z, M, V is hydrogen, X, Y is
N, U is
When, its structural formula is:
when X, Y, Z, M, V is hydrogen, W is
N, U is
When, its structural formula is:
when X, Y, M, V is hydrogen, W, Z is
N, U is
When, its structural formula is:
when W, Z, M, V is hydrogen, X is
Y, N, U is
When, its structural formula is:
when X, Y, M, V is hydrogen, W is
Z, N, U is
When, its structural formula is:
when W, Y, Z, N, U is hydrogen, X is
M, V is
When, its structural formula is:
when W, Z, N, U is hydrogen, X, Y is
M, V is
When, its structural formula is:
when X, Y, Z, N, U is hydrogen, W is
M, V is
When, its structural formula is:
when X, Y, N, U is hydrogen, W, Z is
M, V is
When, its structural formula is:
when W, Z, M, V is hydrogen, X is
Y, N, U is
When, its structural formula is:
when X, Y, N, U is hydrogen, W is
Z, M, V is
When, its structural formula is:
the second embodiment is as follows: the synthesis method of the phosphino-oxygen-group-modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material comprises the following steps:
mixing 0.8-1.2 mmol of 2, 9-dibromo-phenanthroline-5, 6-dione or 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of reaction precursor and 5-10 ml of ethanol, reacting at 80 ℃ for 48 hours, extracting with water and dichloromethane, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate as an eluent to obtain an intermediate;
secondly, taking 1mmol of the intermediate synthesized in the step one, 0.05mmol of palladium acetate, 1-10 mmol of sodium acetate, 1mmol of diphenylphosphine and 5-10 ml of N, N-dimethylformamide, mixing, reacting at 150 ℃ for 48H, and adding 5mmol of H2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as eluent column chromatography to obtain the phosphino group modified bipyridyl phenazinyl red/near infrared thermal excitation delay fluorescent material.
The third concrete implementation mode: the difference between this embodiment and the second embodiment is that in the first step, the reaction precursor is N4', N4' -diphenyl- [1,1 '-biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1 '-biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4 "-tetraphenyl [1, 1': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1 "-terphenyl ] -2', 3', 4, 4" -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide, (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide, N4', N4' -diphenyl- [1,1' -biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1' -biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1' -terphenyl ] -2', 3', 4,4' -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide or (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third difference between the present embodiment and the present embodiment is that the group provided by the precursor in the first step is
The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: this embodiment differs from one of the second to fourth embodiments in that the group provided by the intermediate in step two is
The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the difference between the second embodiment and the fifth embodiment is that 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione or 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of reaction precursor and 10ml of ethanol are mixed in the first step and reacted at 80 ℃ for 48 hours. The rest is the same as one of the second to fifth embodiments.
The seventh embodiment: this embodiment differs from one of the second to sixth embodiments in that in step two, 1mmol of the intermediate, 0.05mmol of palladium acetate, 1mmol of sodium acetate, 1mmol of diphenylphosphine and 10ml of N, N-dimethylformamide are mixed and reacted at 150 ℃ for 48 h. The rest is the same as one of the second to sixth embodiments.
Detailed description of the inventionThe formula eight: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 1 is obtained. The rest is the same as the second embodiment.
The specific implementation method nine: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 2 is obtained. The rest is the same as the second embodiment.
The detailed implementation mode is ten: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 3 is obtained. The rest is the same as the second embodiment.
The concrete implementation mode eleven: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 4 is obtained. Other toolsThe second embodiment is the same.
The specific implementation mode twelve: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 5 is obtained. The rest is the same as the second embodiment.
The specific implementation mode is thirteen: the second difference between the present embodiment and the specific embodiment is that 2, 9-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 6 is obtained. The rest is the same as the second embodiment.
The specific implementation mode is fourteen: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 7 is obtained. The rest is the same as the second embodiment.
The concrete implementation mode is fifteen: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 8 is obtained. The rest is the same as the second embodiment.
The specific implementation mode is sixteen: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 9 is obtained. The rest is the same as the second embodiment.
Seventeenth embodiment: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 10 is obtained. The rest is the same as the second embodiment.
The specific implementation mode is eighteen: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Intermediate use of step two
Compound 11 is obtained. The rest is the same as the second embodiment.
The detailed embodiment is nineteen: the second difference between the present embodiment and the specific embodiment is that 3, 8-dibromo-phenanthroline-5, 6-dione is used in the first step, and the precursor is used
Step twoUse of intermediate
Compound 12 is obtained. The rest is the same as the second embodiment.
The specific implementation mode twenty: the phosphino-oxygen group modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material described in the first and second embodiments is used for an organic electroluminescent device.
The specific implementation mode is twenty one: the difference between the embodiment and the eighth embodiment is that the phosphino-oxygen group modified bipyridyl phenazine based red/near-infrared thermal excitation delayed fluorescence material is applied as follows:
the method comprises the steps of firstly manufacturing a conducting layer, then evaporating a hole transport layer material on the conducting layer, evaporating a doping body luminescent layer of a phosphino-oxygen group modified bipyridyl-phenazine-based red light/near infrared thermal excitation delay fluorescent material and a main material on the hole transport layer, evaporating an electron transport layer material on the luminescent layer, and finally evaporating a second conducting layer. The rest is the same as the embodiment twenty.
Specific embodiment twenty-two: the difference between the embodiment and the eighth embodiment is that the dopant is doped with a bipyridyl phenazinyl red/near infrared thermal excitation delay fluorescent material modified by CBP and phosphine oxide groups. The rest is the same as the embodiment twenty.
Specific embodiment twenty-three: the difference between the embodiment and the eighth embodiment is that the phosphino-oxygen group modified bipyridyl phenazine based red/near-infrared thermal excitation delayed fluorescence material is applied as follows:
firstly, evaporating Indium Tin Oxide (ITO) on a glass or plastic substrate to be used as an anode conducting layer, wherein the thickness is 1-100 nm;
secondly, evaporating a material NPB on the anode conducting layer to be used as a hole transport layer, wherein the thickness of the hole transport layer is 2-10 nm;
thirdly, evaporating a mixture of the CBP and the compounds 1-6 on the hole transport layer to be used as a light-emitting layer, wherein the thickness of the mixture is 20-40 nm;
evaporating a material TPBi on the luminous layer to be used as an electron transmission layer, wherein the thickness of the TPBi is 5-50 nm;
fifthly, evaporating metal (Al) on the electron transport layer to serve as a cathode conducting layer, wherein the thickness of the cathode conducting layer is 1-100 nm, and packaging to obtain the electroluminescent device.
Twenty-four specific embodiments: twenty-three differences in the detailed description of this embodiment are that the material of the light-emitting layer described in step three is a mixture of CBP and compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 11, or compound 12, where the mass concentration of compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 11, or compound 12 is 5%.
The following experiments are adopted to verify the effect of the invention:
experiment one: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 1 is realized by the following steps:
firstly, mixing 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of N4', N4' -diphenyl- [1,1 '-biphenyl ] -3,4,4' -triamine and 10ml of ethanol, reacting at 80 ℃ for 48h, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4- (3, 6-dibromo-bipyridyl [3, 2-a: 2', 3' -c ] phenazine-11-yl) -N, N-diphenylaniline;
secondly, taking the product synthesized in the step one, namely 4- (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-11-yl) -N, N-diphenylaniline 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as eluent to obtain the compound 1.
4- (3, 6-Didibromodipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-11-yl) -N, N-diphenylaniline with the structure
4- (3, 6-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to experiment one]Phenazine-11-yl) -N, N-diphenylaniline, the data of its time-of-flight mass spectrum are: 683(100) M/z (%) [ M+](ii) a The data for elemental analysis were: molecular formula C36H21Br2N5The theoretical value is as follows: c, 63.27; h, 3.10; n, 10.25; measured value: c, 63.29; h, 3.11; n, 10.22.
The data of the flight time mass spectrum of the compound 1 prepared in the second step are as follows: m/z (%) < 925(100) < M >+](ii) a The data for elemental analysis were: molecular formula C60H41N5O2P2The theoretical value is as follows: c, 77.83; h, 4.46; n, 7.56; measured value: c, 77.85; h, 4.44; n, 7.56.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 1 obtained in the experiment is shown in figure 1.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 1 obtained in the experiment is shown in fig. 2, and the chart shows that the cracking temperature of the compound 1 reaches 380 ℃.
Experiment two: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 2 is realized by the following steps:
firstly, mixing 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of N4', N4' -diphenyl- [1,1 '-biphenyl ] -2,3,4' -triamine and 10ml of ethanol, reacting at 80 ℃ for 48h, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4- (3, 6-dibromo-bipyridyl [3, 2-a: 2', 3' -c ] phenazine-10-yl) -N, N-diphenylaniline;
secondly, taking the product synthesized in the step one, namely 4- (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-10-yl) -N, N-diphenylaniline 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmolMixing with 10ml N, N-dimethylformamide, reacting at 150 deg.C for 48H, adding 5mmol H2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 2.
4- (3, 6-Didibromodipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-10-yl) -N, N-diphenylaniline with the structure
4- (3, 6-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to experiment one]Phenazine-10-yl) -N, N-diphenylaniline, the data of its time-of-flight mass spectrum are: 683(100) M/z (%) [ M+](ii) a The data for elemental analysis were: molecular formula C36H21Br2N5The theoretical value is as follows: c, 63.27; h, 3.10; n, 10.25; measured value: c, 63.25; h, 3.11; n, 10.26.
The data of the time-of-flight mass spectrum of the compound 2 prepared in the second step are as follows: m/z (%) < 925(100) < M >+](ii) a The data for elemental analysis were: molecular formula C60H41N5O2P2The theoretical value is as follows: c, 77.83; h, 4.46; n, 7.56; measured value: c, 77.85; h, 4.44; n, 7.56.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 2 obtained in the experiment is shown in FIG. 3.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material compound 2 obtained in the experiment is shown in fig. 4, and the graph shows that the cracking temperature of the compound 2 reaches 370 ℃.
Experiment three: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 3 is realized by the following steps:
1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of N4, N4, N4', N4 ″ -tetraphenyl [1, 1': mixing 2', 1' -terphenyl ] -4,4', 5' -tetramine and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4,4' - (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c ] phenazine-11, 12-diyl) bis (N, N-diphenylaniline);
secondly, taking the product synthesized in the first step, namely 4,4' - (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml were mixed, reacted at 150 ℃ for 48 hours, and 5mmol of H was added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 3.
This experimental procedure I4, 4' - (3, 6-dibromodipyridyl [3, 2-a: 2', 3' -c ]]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) having the structure
4,4' - (3, 6-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to step one of experiment one]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) having time-of-flight mass spectral data: m/z (%) < 926 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C54H34Br2N6The theoretical value is as follows: c, 69.99; h, 3.70; n, 9.07; measured value: c, 69.97; h, 3.72; and N, 9.07.
The data of the time-of-flight mass spectrum of the compound 3 prepared in the second step are as follows: m/z (%) < 1169 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C78H54N6O2P2The theoretical value is as follows: c, 80.12; h, 4.66; n, 7.19; measured value: c, 80.14; h, 4.66; and N, 7.17.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 3 obtained in the experiment is shown in FIG. 5.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 3 obtained in the experiment is shown in fig. 6, and the chart shows that the cracking temperature of the compound 3 reaches 409 ℃.
Experiment four: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 4 is realized by the following steps:
1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of N4, N4, N4', N4 ″ -tetraphenyl [1, 1': mixing 4', 1' -terphenyl ] -2', 3', 4,4 '-tetramine and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4,4' - (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c ] phenazine-10, 13-diyl) bis (N, N-diphenylaniline);
secondly, taking the product synthesized in the first step, namely 4,4' - (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml were mixed, reacted at 150 ℃ for 48 hours, and 5mmol of H was added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as eluent to obtain the compound 4.
4,4' - (3, 6-dibromo-dipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) having the structure
4,4' - (3, 6-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to step one of experiment one]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) with time-of-flight mass spectral data: m/z (%) < 926 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C54H34Br2N6The theoretical value is as follows: c, 69.99; h, 3.70; n, 9.07; measured value: and C,69.97；H,3.71；N,9.08。
The data of the time-of-flight mass spectrum of the compound 4 prepared in the second step are as follows: m/z (%) < 1169 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C78H54N6O2P2The theoretical value is as follows: c, 80.12; h, 4.66; n, 7.19; measured value: c, 80.13; h, 4.67; and N, 7.17.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 4 obtained in the experiment is shown in FIG. 7.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 4 obtained in the experiment is shown in fig. 8, and the graph shows that the cracking temperature of the compound 4 reaches 419 ℃.
Experiment five: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 5 is realized by the following steps:
firstly, mixing 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of (4, 5-diamino-4 '- (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenyl phosphine oxide and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as eluent column chromatography to obtain (3, 6-dibromo-12- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c ] phenazine-11-yl) diphenyl phosphine oxide;
secondly, taking the product (3, 6-dibromo-12- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c) synthesized in the step one]Phenazine-11-yl) diphenylphosphine oxide 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 5.
(3, 6-dibromo-12- (4- (diphenylamino) phenyl) bipyridino [3 ] prepared in this experimental procedure one,2-a：2'，3'-c]phenazine-11-yl) diphenylphosphine oxide of the structure
(3, 6-dibromo-12- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared according to Example one step]Phenazin-11-yl) diphenylphosphine oxide with data of time-of-flight mass spectrum: m/z (%) < 883 >+](ii) a The data for elemental analysis were: molecular formula C48H30Br2N5OP, theoretical value: c, 65.25; h, 3.42; n, 7.93; measured value: c, 65.23; h, 3.44; and N, 7.93.
The data of the time-of-flight mass spectrum of the compound 5 prepared in the second step are as follows: m/z (%) < 1126(100) < M >+](ii) a The data for elemental analysis were: molecular formula C72H50N5O3P3The theoretical value is as follows: c, 79.43; h, 4.44; n, 9.65; measured value: c, 79.42; h, 4.43; n, 9.67.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 5 obtained in the experiment is shown in FIG. 9.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 5 obtained in the experiment is shown in fig. 10, and the chart shows that the cracking temperature of the compound 5 reaches 449 ℃.
Experiment six: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material compound 6 is realized by the following steps:
firstly, mixing 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione, 1mmol of (2, 3-diamino-4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenyl phosphine oxide and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain (3, 6-dibromo-13- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c ] phenazine-10-yl) diphenyl phosphine oxide;
secondly, taking the product (3, 6-dibromo-13- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c) synthesized in the step one]Phenazine-10-yl) diphenylphosphine oxide 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 6.
(3, 6-dibromo-13- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared in Experimental step one]Phenazine-10-yl) diphenylphosphine oxide of the structure
(3, 6-dibromo-13- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared according to Example one step]Phenazin-10-yl) diphenylphosphine oxide with data of time-of-flight mass spectrum: m/z (%) < 883 >+](ii) a The data for elemental analysis were: molecular formula C48H30Br2N5OP, theoretical value: c, 65.25; h, 3.42; n, 7.93; measured value: c, 65.23; h, 3.44; and N, 7.93.
The data of the time-of-flight mass spectrum of the compound 6 prepared in the second step are as follows: m/z (%) < 1126(100) < M >+](ii) a The data for elemental analysis were: molecular formula C72H50N5O3P3The theoretical value is as follows: c, 79.43; h, 4.44; n, 9.65; measured value: c, 79.40; h, 4.45; n, 9.67.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 6 obtained in the experiment is shown in FIG. 11.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 6 obtained in the experiment is shown in fig. 12, and the graph shows that the cracking temperature of the compound 6 reaches 428 ℃.
Experiment seven: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 7 is realized by the following steps:
firstly, mixing 1mmol of 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of N4', N4' -diphenyl- [1,1 '-biphenyl ] -3,4,4' -triamine and 10ml of ethanol, reacting at 80 ℃ for 48h, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4- (2, 7-dibromo-bipyridyl [3, 2-a: 2', 3' -c ] phenazine-11-yl) -N, N-diphenylaniline;
secondly, taking the product synthesized in the first step, namely 4- (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-11-yl) -N, N-diphenylaniline 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as eluent to obtain the compound 7.
4- (2, 7-Didibromodipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-11-yl) -N, N-diphenylaniline with the structure
4- (2, 7-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to experiment one]Phenazine-11-yl) -N, N-diphenylaniline, the data of its time-of-flight mass spectrum are: 683(100) M/z (%) [ M+](ii) a The data for elemental analysis were: molecular formula C36H21Br2N5The theoretical value is as follows: c, 63.27; h, 3.10; n, 10.25; measured value: c, 63.23; h, 3.12; n, 10.27.
The data of the time-of-flight mass spectrum of the compound 7 prepared in the second step are as follows: m/z (%) < 925(100) < M >+](ii) a The data for elemental analysis were: molecular formula C60H41N5O2P2The theoretical value is as follows: c, 77.83; h, 4.46; n, 7.56; measured value: c, 77.88; h, 4.43; n, 7.54.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 7 obtained in the experiment is shown in fig. 13.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 7 obtained in the experiment is shown in fig. 14, and the chart shows that the cracking temperature of the compound 7 reaches 431 ℃.
Experiment eight: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 8 is realized by the following steps:
firstly, mixing 1mmol of 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of N4', N4' -diphenyl- [1,1 '-biphenyl ] -2,3,4' -triamine and 10ml of ethanol, reacting at 80 ℃ for 48h, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4- (2, 7-dibromo-bipyridyl [3, 2-a: 2', 3' -c ] phenazine-10-yl) -N, N-diphenylaniline;
secondly, taking the product synthesized in the first step, namely 4- (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-10-yl) -N, N-diphenylaniline 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 8.
4- (2, 7-Didibromodipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-10-yl) -N, N-diphenylaniline with the structure
4- (2, 7-Didibromodipyrido [3, 2-a: 2', 3' -c ] prepared according to experiment one]Phenazine-10-yl) -N, N-diphenylaniline, the data of its time-of-flight mass spectrum are: 683(100) M/z (%) [ M+](ii) a The data for elemental analysis were: molecular formula C36H21Br2N5The theoretical value is as follows: c, 63.27; h, 3.10; n, 10.25; measured value: c, 63.29; h, 3.11; n, 10.21.
The data of the time-of-flight mass spectrum of the compound 8 prepared in the second step are as follows: m/z (%) < 925(100) < M >+](ii) a The data for elemental analysis were: molecular formula C60H41N5O2P2The theoretical value is as follows: c, 77.83; h, 4.46; n, 7.56; measured value: c, 77.80; h, 4.48; and N, 7.57.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 8 obtained in the experiment is shown in FIG. 15.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 8 obtained in the experiment is shown in fig. 16, and the graph shows that the cracking temperature of the compound 8 reaches 430 ℃.
Experiment nine: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 9 is realized by the following steps:
1mmol of 3, 8-dibromophenanthroline-5, 6-dione, 1mmol of N4, N4, N4', N4' -tetraphenyl [1,1 ': mixing 2', 1' -terphenyl ] -4,4', 5' -tetramine and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4,4' - (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c ] phenazine-11, 12-diyl) bis (N, N-diphenylaniline);
secondly, taking the product synthesized in the first step, namely 4,4' - (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml were mixed, reacted at 150 ℃ for 48 hours, and 5mmol of H was added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 9.
The true bookTest procedure I4, 4' - (2, 7-dibromodipyridyl [3, 2-a: 2', 3' -c ]]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) having the structure
4,4' - (2, 7-Didibromobipyridino [3, 2-a: 2', 3' -c) prepared according to step one of experiment one]Phenazine-11, 12-diyl) bis (N, N-diphenylaniline) having time-of-flight mass spectral data: m/z (%) < 926 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C54H34Br2N6The theoretical value is as follows: c, 69.99; h, 3.70; n, 9.07; measured value: c, 69.99; h, 3.72; and N, 9.05.
The data of the time-of-flight mass spectrum of the compound 9 prepared in the second step are as follows: m/z (%) < 1169 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C78H54N6O2P2The theoretical value is as follows: c, 80.12; h, 4.66; n, 7.19; measured value: c, 80.14; h, 4.64; and N, 7.19.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 9 obtained in the experiment is shown in fig. 17.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 9 obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the compound 9 reaches 498 ℃.
Experiment ten: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material compound 10 is realized by the following steps:
1mmol of 3, 8-dibromophenanthroline-5, 6-dione, 1mmol of N4, N4, N4', N4' -tetraphenyl [1,1 ': mixing 4', 1' -terphenyl ] -2', 3', 4,4 '-tetramine and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography to obtain 4,4' - (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c ] phenazine-10, 13-diyl) bis (N, N-diphenylaniline);
secondly, taking the product synthesized in the first step, namely 4,4' - (2, 7-dibromo-dipyridyl [3, 2-a: 2', 3' -c)]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml were mixed, reacted at 150 ℃ for 48 hours, and 5mmol of H was added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as eluent to obtain the compound 10.
4,4' - (2, 7-dibromodipyridyl [3, 2-a: 2', 3' -c ] prepared in the first experimental step]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) having the structure
4,4' - (2, 7-Didibromobipyridino [3, 2-a: 2', 3' -c) prepared according to step one of experiment one]Phenazine-10, 13-diyl) bis (N, N-diphenylaniline) with time-of-flight mass spectral data: m/z (%) < 926 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C54H34Br2N6The theoretical value is as follows: c, 69.99; h, 3.70; n, 9.07; measured value: c, 69.94; h, 3.72; and N, 9.10.
The data of the time-of-flight mass spectrum of the compound 10 prepared in the second step are as follows: m/z (%) < 1169 > (100) < M >+](ii) a The data for elemental analysis were: molecular formula C78H54N6O2P2The theoretical value is as follows: c, 80.12; h, 4.66; n, 7.19; measured value: c, 80.16; h, 4.63; and N, 7.18.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 10 obtained in the experiment is shown in fig. 19.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 10 obtained in the experiment is shown in fig. 20, and the graph shows that the cracking temperature of the compound 10 reaches 490 ℃.
Experiment eleven: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 11 is realized by the following steps:
firstly, mixing 1mmol of 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of (4, 5-diamino-4 '- (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenyl phosphine oxide and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as eluent column chromatography to obtain (2, 7-dibromo-12- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c ] phenazine-11-yl) diphenyl phosphine oxide;
secondly, taking the product (2, 7-dibromo-12- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c) synthesized in the step one]Phenazine-11-yl) diphenylphosphine oxide 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as eluent to obtain compound 11.
(2, 7-dibromo-12- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared in Experimental step one]Phenazine-11-yl) diphenylphosphine oxide of the structure
(2, 7-dibromo-12- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared according to Example one step]Phenazin-11-yl) diphenylphosphine oxide with data of time-of-flight mass spectrum: m/z (%) < 883 >+](ii) a The data for elemental analysis were: molecular formula C48H30Br2N5OP, theoretical value: c, 65.25; h, 3.42; n, 7.93; measured value: c, 65.21; h, 3.44; and N, 7.95.
The data of the time-of-flight mass spectrum of the compound 11 prepared in the second step are as follows: m/z (%) < 1126(100) < M >+](ii) a The data for elemental analysis were: molecular formula C72H50N5O3P3The theoretical value is as follows: c, 79.43; h, 4.44; n, 9.65; measured value: c, 79.49; h, 4.40; and N, 9.63.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 11 obtained in the experiment is shown in fig. 21.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 11 obtained in the experiment is shown in fig. 22, and the graph shows that the cracking temperature of the compound 11 reaches 516 ℃.
Experiment twelve: the synthesis method of the experimental phosphine oxide group modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material compound 12 is realized by the following steps:
firstly, mixing 1mmol of 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of (2, 3-diamino-4 '- (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenyl phosphine oxide and 10ml of ethanol, reacting for 48h at 80 ℃, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as eluent column chromatography to obtain (2, 7-dibromo-13- (4- (diphenylamino) phenyl) bipyridyl [3, 2-a: 2', 3' -c ] phenazine-10-yl) diphenyl phosphine oxide;
secondly, taking the product (2, 7-dibromo-13- (4- (diphenylamino) phenyl) dipyridyl [3, 2-a: 2', 3' -c) synthesized in the step one]Phenazine-10-yl) diphenylphosphine oxide 1mmol, palladium acetate 0.05mmol, sodium acetate 1mmol, diphenylphosphine 1mmol and N, N-dimethylformamide 10ml are mixed, reacted at 150 ℃ for 48H, and then 5mmol of H is added2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing organic solvent, and purifying by eluting with mixed solvent of dichloromethane and ethyl acetate to obtain compound 12.
(2, 7-dibromo-13- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared in Experimental step one]Phenazine-10-yl) diphenylphosphine oxide of the structure
(2, 7-dibromo-13- (4- (diphenylamino) phenyl) bipyridino [3, 2-a: 2', 3' -c) prepared according to Example one step]Phenazin-10-yl) diphenylphosphine oxide with data of time-of-flight mass spectrum: m/z (%) < 883 >+](ii) a The data for elemental analysis were: molecular formula C48H30Br2N5OP, theoretical value: c, 65.25; h, 3.42; n, 7.93; measured value: c, 65.20; h, 3.45; and N, 7.95.
The data of the time-of-flight mass spectrum of the compound 12 prepared in the second step are as follows: m/z (%) < 1126(100) < M >+](ii) a The data for elemental analysis were: molecular formula C72H50N5O3P3The theoretical value is as follows: c, 79.43; h, 4.44; n, 9.65; measured value: c, 79.46; h, 4.42; and N, 9.64.
The ultraviolet fluorescence spectrum of the phosphino-oxygen group-modified bipyridyl-phenazine based red/near-infrared thermal excitation delayed fluorescence material compound 12 obtained in the experiment is shown in fig. 23.
The thermogravimetric analysis spectrogram of the phosphino-oxo-group-modified bipyridylphenozinyl red-light/near-infrared thermal excitation delayed fluorescence material compound 12 obtained in the experiment is shown in fig. 24, and the chart shows that the cracking temperature of the compound 12 reaches 511 ℃.
The first application embodiment: in this embodiment, an electroluminescent red TADF device prepared by using the phosphino-oxygen group-modified bipyridylphenozinyl red/near-infrared thermally-excited delayed fluorescence material compound 1 as a light-emitting layer material is prepared according to the following steps:
the luminescent layer is a doping body of a compound 1 and 4,4' -bis (9-Carbazole) Biphenyl (CBP), and is formed by evaporation, and the thickness is 40 nm. A hole transport layer (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, NPB) with a thickness of 10nm was deposited between the anode (indium tin oxide ITO) and the light-emitting layer. The material used for the electron transport layer is 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), and the thickness of the film is 10 nm. The electrode material is aluminum and the thickness is 100 nm. The structure of the device is ITO/NPB (10nm)/CBP 1(40nm)/TPBi (10nm)/Al (100nm)
The voltage-current density curve of the electroluminescent red TADF device prepared by using compound 1 in this example is shown in fig. 25, from which it can be seen that compound 1 has semiconductor characteristics and the threshold voltage thereof is 9V.
The voltage-luminance relationship curve of the electroluminescent red TADF device prepared by the compound 1 in the embodiment is shown in FIG. 26, and the maximum luminance of the device can reach 5253 cd.m-2。
The current density-current efficiency curve of the electroluminescent red TADF device prepared by the compound 1 in the example is shown in FIG. 27, and the current density of the device is 50.99 mA-cm-2When the current efficiency reaches the maximum value of 5.07 cd.A-1。
The current density-power efficiency curve of the electroluminescent red TADF device prepared by the compound 1 in the example is shown in FIG. 28, and the current density of the device is 50.99 mA-cm-2When the power efficiency reaches the maximum value of 1.35 lm.W-1。
The current density-external quantum efficiency curve of the electroluminescent red TADF device prepared by the compound 1 in the embodiment is shown in FIG. 29, and the graph shows that the device has the current density of 50.99mA cm-2Then, a maximum external quantum efficiency of 7.47% was obtained.
The electroluminescence spectrum of the electroluminescent red TADF device prepared by the compound 1 in the embodiment is shown in FIG. 30, and the electroluminescence peak of the device is at 660 nm.
Claims (10)
1. The phosphino-oxygen-group-modified bipyridyl phenazine-based red/near-infrared thermal excitation delayed fluorescence material is characterized in that the phosphino-oxygen-group-modified bipyridyl phenazine-based red/near-infrared thermal excitation delayed fluorescence material has the following structural formula:
wherein W, Y, Z, M, V is hydrogen and X is
N, U is
W, Z, M, V is hydrogen, X, Y is
N, U is
X, Y, Z, M, V is hydrogen, W is
N, U is
X, Y, M, V is hydrogen, W, Z is
N, U is
W, Z, M, V is hydrogen, X is
Y, N, U is
X, Y, M, V is hydrogen, W is
Z, N, U is
W, Y, Z, N, U is hydrogen, X is
M, V is
W, Z, N, U is hydrogen, X, Y is
M, V is
X, Y, Z, N, U is hydrogen, W is
M, V is
X, Y, N, U is hydrogen, W, Z is
M, V is
W, Z, M, V is hydrogen, X is
Y, N, U is
X, Y, N, U is hydrogen, W is
Z, M, V is
2. The method for synthesizing the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material as claimed in claim 1, wherein the method for synthesizing the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material is carried out according to the following steps:
mixing 0.8-1.2 mmol of 2, 9-dibromo-phenanthroline-5, 6-dione or 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of reaction precursor and 5-10 ml of ethanol, reacting at 80 ℃ for 48 hours, extracting with water and dichloromethane, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate as an eluent to obtain an intermediate;
secondly, taking 1mmol of the intermediate synthesized in the step one, 0.05mmol of palladium acetate, 1-10 mmol of sodium acetate, 1mmol of diphenylphosphine and 5-10 ml of N, N-dimethylformamide, mixing, reacting at 150 ℃ for 48H, and adding 5mmol of H2O2Oxidizing, extracting with water and dichloromethane, combining organic layers, drying, removing the organic solvent, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as eluent column chromatography to obtain the phosphino group modified bipyridyl phenazinyl red/near infrared thermal excitation delay fluorescent material.
3. The method for synthesizing the phosphino-oxy-group-modified bipyridylphenozinyl red/near-infrared thermally-excited delayed fluorescence material as claimed in claim 2, wherein the reaction precursor in the first step is N4', N4' -diphenyl- [1,1 '-biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1 '-biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4 "-tetraphenyl [1, 1': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1 "-terphenyl ] -2', 3', 4, 4" -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide, (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide, N4', N4' -diphenyl- [1,1' -biphenyl ] -3,4,4' -triamine, N4', N4' -diphenyl- [1,1' -biphenyl ] -2,3,4' -triamine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 2', 1 "-terphenyl ] -4,4', 4", 5' -tetramine, N4, N4, N4', N4 "-tetraphenyl [1,1 ': 4', 1' -terphenyl ] -2', 3', 4,4' -tetramine, (4, 5-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -2-yl) diphenylphosphine oxide or (2, 3-diamino-4 ' - (diphenylamino) - [1,1' -biphenyl ] -4-yl) diphenylphosphine oxide.
4. The method for synthesizing the phosphino-oxygen-group-modified bipyridyl-phenazinyl red/near-infrared thermal excitation delayed fluorescence material according to claim 2 or 3, wherein the group provided by the reaction precursor in the first step is
5. The method for synthesizing the phosphino-oxygen-group-modified bipyridyl-phenazinyl red/near infrared thermal excitation delayed fluorescence material according to claim 2, wherein the group provided by the intermediate in the second step is
6. The synthesis method of the phosphino-oxygen group-modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material according to claim 2, characterized in that in step one, 1mmol of 2, 9-dibromo-phenanthroline-5, 6-dione or 3, 8-dibromo-phenanthroline-5, 6-dione, 1mmol of reaction precursor and 10ml of ethanol are mixed and reacted at 80 ℃ for 48 h.
7. The synthesis method of the phosphino-oxy-group-modified bipyridyl phenazinyl red/near infrared thermal excitation delayed fluorescence material as claimed in claim 2, wherein in step two, 1mmol of intermediate, 0.05mmol of palladium acetate, 1mmol of sodium acetate, 1mmol of diphenylphosphine and 10ml of N, N-dimethylformamide are mixed and reacted at 150 ℃ for 48 h.
8. The use of the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material as claimed in claim 1, wherein the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material is used in an organic electroluminescent device.
9. The application of the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material according to claim 8, wherein the phosphino group-modified bipyridyl phenazine based red/near infrared thermal excitation delayed fluorescence material is applied as follows:
the method comprises the steps of firstly manufacturing a conducting layer, then evaporating a hole transport layer material on the conducting layer, evaporating a doping body luminescent layer of a phosphino-oxygen group modified bipyridyl-phenazine-based red light/near infrared thermal excitation delay fluorescent material and a main material on the hole transport layer, evaporating an electron transport layer material on the luminescent layer, and finally evaporating a second conducting layer.
10. The application of the phosphino group modified bipyridyl phenazine based red/near infrared thermal excitation delay fluorescent material as claimed in claim 8, wherein the dopant is a CBP doped with the phosphino group modified bipyridyl phenazine based red/near infrared thermal excitation delay fluorescent material.
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