CN114195781A - Pyridopyrazine compound and preparation method and application thereof - Google Patents
Pyridopyrazine compound and preparation method and application thereof Download PDFInfo
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- CN114195781A CN114195781A CN202111600351.2A CN202111600351A CN114195781A CN 114195781 A CN114195781 A CN 114195781A CN 202111600351 A CN202111600351 A CN 202111600351A CN 114195781 A CN114195781 A CN 114195781A
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- CN
- China
- Prior art keywords
- compound
- substituent
- pyridopyrazine
- layer
- organic electroluminescent
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- -1 Pyridopyrazine compound Chemical class 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 52
- YEYHFKBVNARCNE-UHFFFAOYSA-N pyrido[2,3-b]pyrazine Chemical compound N1=CC=NC2=CC=CN=C21 YEYHFKBVNARCNE-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract description 14
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims abstract description 10
- 125000006617 triphenylamine group Chemical group 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 133
- 238000002156 mixing Methods 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 230000005525 hole transport Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- JUFLTGRGLUCRCU-UHFFFAOYSA-N ethanediimidoyl dicyanide Chemical compound N#CC(=N)C(=N)C#N JUFLTGRGLUCRCU-UHFFFAOYSA-N 0.000 claims description 15
- 230000000903 blocking effect Effects 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002346 layers by function Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 9
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical class NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 9
- 238000007363 ring formation reaction Methods 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 3
- 229920001088 polycarbazole Polymers 0.000 claims description 3
- 229920002098 polyfluorene Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 4
- PMSVVUSIPKHUMT-UHFFFAOYSA-N cyanopyrazine Chemical compound N#CC1=CN=CC=N1 PMSVVUSIPKHUMT-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 40
- 230000007704 transition Effects 0.000 abstract description 7
- 229950000688 phenothiazine Drugs 0.000 abstract description 6
- 238000004776 molecular orbital Methods 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 3
- 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 abstract description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 76
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000005160 1H NMR spectroscopy Methods 0.000 description 39
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- 238000006862 quantum yield reaction Methods 0.000 description 38
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 12
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 12
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 12
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 12
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 12
- 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 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 10
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- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 8
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
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- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
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- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 3
- WDTOXRACOCNQRB-UHFFFAOYSA-N 2,5-dibromopyridine-3,4-diamine Chemical compound NC1=C(Br)C=NC(Br)=C1N WDTOXRACOCNQRB-UHFFFAOYSA-N 0.000 description 3
- RHPVVNRNAHRJOQ-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1NC1=CC=C(C)C=C1 RHPVVNRNAHRJOQ-UHFFFAOYSA-N 0.000 description 3
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
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- WZGCATLRXSAEOB-UHFFFAOYSA-N 2-(naphthalen-1-ylmethyl)-7-phenyl-7h-pyrazolo[4,3-e][1,2,4]triazolo[1,5-c]pyrimidine Chemical compound C=1C=CC2=CC=CC=C2C=1CC(=NN1C=NC=23)N=C1C=2C=NN3C1=CC=CC=C1 WZGCATLRXSAEOB-UHFFFAOYSA-N 0.000 description 2
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- 239000012265 solid product Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a pyridopyrazine compound and a preparation method and application thereof, and relates to the technical field of organic electroluminescent materials. The pyridopyrazine compound provided by the invention has a structure shown in a formula I. According to the invention, an electron donor group (triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent) is introduced into pyridopyrazine to adjust the front-line molecular orbital level of molecules, so that the luminous color of the compound in a red light region and the triplet-singlet energy level difference delta E of the moleculesSTThe compound is realized to emit red light. Furthermore, having rigid planes in addition to the pyridopyrazine hetero ringsIn addition, the N on the pyridine ring and an electron donor group form an intramolecular hydrogen bond, so that the molecular rigidity is further enhanced, the non-radiative transition rate is reduced, the pyridopyrazine compound has high luminous efficiency, and the pyridopyrazine compound has a good application prospect in an organic electroluminescent device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a pyridopyrazine compound and a preparation method and application thereof.
Background
In 2012, professor chiyaha adachi, kyushu, japan published a title "high efficiency organic light-emitting diodes derived from Delayed Fluorescence" (Hiroki, Uoyama, Kenichi, et al, high efficiency Fluorescence light-emitting diodes from Delayed Fluorescence [ J ]. Nature,2012,492(dec.13tn.7428): 234; "234;) which illustrates the concept of Thermally Activated Delayed Fluorescence (TADF), increased the theoretical internal quantum efficiency of the fluorescent material to 100%, has great commercial potential, and is considered as a key technology for next generation OLED display. Adachi et al report that high-efficiency electrons based on the TADF principle are used as a receptor type luminescent material, and make outstanding contribution to the field of electroluminescent devices and the development of organic electronics.
TADF materials currently present two issues that need to be addressed: (1) the efficiency roll-off of an electroluminescent device based on the TADF luminescent material is serious under high brightness, which can seriously affect the service life, the use stability and the practicability of the device (the device can be used for outdoor illumination when the brightness reaches 5000 cd/m); (2) in the development of the TADF material with three primary colors of red, green and blue, the high-performance TADF material with red light is still very deficient. The reason is that to ensure a material with an efficient TADF process, it is necessary to ensure the molecular singlet S1And triplet state T1The energy difference between them is as small as possible, i.e. the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the molecular structure need to be separated in space as much as possible, but such a structure will reduce the radiative transition rate, resulting in a reduced fluorescence quantum yield of the material. Therefore, how to design molecular structure to solve S1And T1The contradiction between small energy difference and high radiation transition rate is the key point for developing high-performance red TADF materials.
To solve the above problems, the design of the red TADF material is based on the following molecular design principles: (1) selecting a suitable combination of donor and acceptor groups to obtain the electronic structures of the separated HOMO and LUMO,realize smaller S1And T1Energy range delta EST (generally less than 0.1eV), and the rate of anti-gap jumping is improved; (2) selecting a proper connection mode between electron donor and acceptor groups, balancing the degrees of spatial separation and superposition of HOMO and LUMO, and improving the radiation transition rate; (3) the molecules with rigid structures are selected, and the molecules have large steric hindrance, so that non-radiative transition can be inhibited, and the fluorescence emission efficiency is improved.
The N-substituted aromatic heterocyclic compound with a condensed ring structure is used as a good electron acceptor group, has a rigid plane structure, can be connected with different acceptor groups through Suzuki reaction and Ullmann reaction, and is widely applied to donor-acceptor type organic red light TADF materials. The material has the advantages of simple synthesis, good thermal stability and the like, but still has the problem of low luminous efficiency.
Disclosure of Invention
In view of this, the present invention provides a pyridopyrazine compound, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pyridopyrazine compound which has a structure shown in a formula I:
in the formula I, R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
Preferably, said R is1And R2Independently comprises hydrogen and any one of the following structures:
the invention provides a preparation method of the pyridopyrazine compound, which comprises the following steps:
under a protective atmosphere, mixing the halogenated pyridodicyanopyrazine, a compound II, a palladium catalyst and an alkaline reagent, and carrying out a coupling reaction to obtain a pyridopyrazine compound with a structure shown in a formula I;
the structural formula of the halogenated pyridodicyanopyrazine is shown in the specification
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time;
the structural formula of the compound II is
In the compound II R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
Preferably, the preparation method of the halogenated pyridodicyanopyrazine comprises the following steps:
mixing diimino butanedinitrile, halogenated diaminopyridine and trifluoroacetic acid, and carrying out cyclization reaction to obtain halogenated pyridodicyanopyrazine;
the structural formula of the halogenated diaminopyridine is shown in the specification
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time.
Preferably, the molar ratio of the halopyridodicyanopyrazine to the compound II is 1: 1.1-3;
the molar ratio of the halogenated pyridodicyanopyrazine to the alkaline reagent is 1: 4-10;
the temperature of the coupling reaction is 80-110 ℃, and the time is 12-24 h.
The invention provides application of the pyridopyrazine compound in the technical scheme or the pyridopyrazine compound obtained by the preparation method in the technical scheme in an organic electroluminescent device.
The invention provides an organic electroluminescent device which comprises a light-emitting layer, an electrode layer and a functional layer, wherein the raw materials for preparing the light-emitting layer comprise the pyridopyrazine compound in the technical scheme or the pyridopyrazine compound obtained by the preparation method in the technical scheme.
Preferably, the raw materials for preparing the light-emitting layer further comprise a host material;
the host material comprises a small molecule host material and/or a high molecule host material;
the micromolecule main body material comprises one or more of 4,4 '-N, N' -dicarbazole biphenyl, 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole, 1,3, 5-tri (2-N-phenyl benzimidazolyl) benzene and 3- (4-diphenyl) -5- (4-tert-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-triazole;
the polymer main body material comprises one or more of polystyrene, polyphenylene, polyvinyl carbazole, polycarbazole and polyfluorene.
Preferably, the functional layer includes one or more layers of a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The invention provides the application of the organic electroluminescent device in the technical scheme in an illuminating light source, a signal lamp, an indication board or a flat panel display.
The invention provides a pyridopyrazine compound with a structure shown in formula I, wherein R in the formula I1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time. According to the invention, an electronegative functional group (triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent) is introduced as an electron donor group to chemically modify 5-position and/or 8-position of pyridopyrazine, the electron donating capability and the connection site of the substituent can influence the intramolecular charge transfer effect and the space distribution of molecular front molecular orbitals, the adjustment of the molecular front molecular orbital energy level is realized, and the luminescent color of the pyridopyrazine compound in a red light region and the triplet-singlet energy level difference Delta E of the molecule are further realizedSTTo obtain the emission wavelength and the molecule Delta ESTThe adjustable luminescent material realizes that the pyridopyrazine compound emits red light. Meanwhile, in the pyridopyrazine compound, besides the pyridopyrazine heterocycle has a rigid planar structure, N on the pyridine ring can form an intramolecular hydrogen bond with an electron donor, so that the molecular rigidity is further enhanced, the non-radiative transition rate is reduced, and the luminous efficiency of the pyridopyrazine compound is improved. The pyridopyrazine compound provided by the invention can emit macroscopically, has high luminous efficiency and has a good application prospect in organic electroluminescent devices. As shown in the test results of the examples, the pyridopyrazine compound provided by the invention has the light-emitting wavelength of 570-730 nm and the fluorescence quantum yield of 3.0-19.8%.
The preparation method provided by the invention is simple to operate, high in product yield, low in price of preparation raw materials, low in production cost and suitable for industrial production.
The invention provides an organic electroluminescent device which comprises a light-emitting layer, wherein the raw material for preparing the light-emitting layer comprises the pyridopyrazine compound in the technical scheme or the pyridopyrazine compound obtained by the preparation method in the technical scheme. In the present invention, the presence of an electron donor group (triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent) in the pyridopyrazine compound enablesCan adjust the front-line molecular orbital energy level of the molecule, and further adjust the luminous color of the pyridopyrazine compound in a red light region and the triplet-singlet energy level difference delta E of the moleculeSTThe compound is realized to emit red light. Meanwhile, except that the pyridopyrazine heterocyclic ring has a rigid planar structure, N on the pyridine ring can form an intramolecular hydrogen bond with an electron donor, so that the molecular rigidity is further enhanced, the nonradiative transition rate is reduced, the luminous efficiency of the pyridopyrazine compound is high, the organic electroluminescent device is high in efficiency and long in service life, and the organic electroluminescent device has a very good application prospect in the aspects of lighting sources, signal lamps, indicators and flat panel displays. As shown in the test results of the examples, the organic electroluminescent device using the pyridopyrazine compound I-1 as the light-emitting layer has the turn-on voltage of 3.9V, the maximum current efficiency of 1.31cd/A and the power efficiency of 1.91 m/W; emitting deep red light with peak position of 690nm and maximum brightness of 1059cd/m2(ii) a The starting voltage of the organic electroluminescent device taking the pyridopyrazine compound I-13 as the luminescent layer is 3.0V, the maximum current efficiency is 3.80cd/A, and the power efficiency is 5.96 m/W; red light emission, peak position 600nm, maximum luminance 6680cd/m2(ii) a The starting voltage of an organic electroluminescent device taking the pyridopyrazine compound I-19 as a light-emitting layer is 4.4V, the maximum current efficiency is 3.92cd/A, and the power efficiency is 7.44 m/W; red light emission, peak position 650nm, maximum luminance 3730cd/m2(ii) a The starting voltage of an organic electroluminescent device taking the pyridopyrazine compound I-1(20 wt%) and TPBI as light-emitting layers is 3.1V, the maximum current efficiency is 5.6cd/A, and the power efficiency is 5.1 lm/W; emitting deep red light with peak position of 668nm and maximum brightness of 3720cd/m2(ii) a The starting voltage of an organic electroluminescent device taking the pyridopyrazine compound I-13(20 wt%) and TPBI as light-emitting layers is 3.1V, the maximum current efficiency is 25.1cd/A, and the power efficiency is 18.5 lm/W; emitting orange red light with peak position of 580nm and maximum brightness of 10700cd/m2(ii) a The starting voltage of an organic electroluminescent device taking the pyridopyrazine compound I-13(20 wt%) and TPBI as light-emitting layers is 3.1V, the maximum current efficiency is 19.8cd/A, and the power efficiency is 18.2 lm/W; red light emission, peak position 600nm, maximum luminance 8950cd/m2。
Drawings
FIG. 1 is a spectrum of an organic electroluminescent device produced in example 38;
FIG. 2 is a spectrum of an organic electroluminescent device produced in example 39;
FIG. 3 is a spectrum of an organic electroluminescent device produced in example 41;
FIG. 4 is a spectrum diagram of an organic electroluminescent device produced in example 42.
Detailed Description
The invention provides a pyridopyrazine compound which has a structure shown in a formula I:
in the formula I, R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
In the present invention, said R1And R2Independently preferably comprises hydrogen and any one of the following structures:
in the present invention, the pyridopyrazine compound preferably has any one of the structures represented by formulas I-1 to I-36:
the invention provides a preparation method of the pyridopyrazine compound in the technical scheme, which comprises the following steps:
under a protective atmosphere, mixing the halogenated pyridodicyanopyrazine, a compound II, a palladium catalyst and an alkaline reagent, and carrying out a coupling reaction to obtain a pyridopyrazine compound with a structure shown in a formula I;
the structural formula of the halogenated pyridodicyanopyrazine is shown in the specification
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time;
the structural formula of the compound II is
In the compound II R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the preparation method of the halopyridodicyanopyrazine preferably comprises the following steps:
mixing diimino butanedinitrile, halogenated diaminopyridine and trifluoroacetic acid, and carrying out cyclization reaction to obtain halogenated pyridodicyanopyrazine;
the structural formula of the halogenated diaminopyridine is shown in the specification
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time.
In the present invention, the diimino succinonitrile is preferably commercially available or homemade, which is well known to those skilled in the art. In the present invention, the method for preparing diimino succinonitrile preferably comprises the steps of: mixing diaminomaleonitrile, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and an organic solvent, and carrying out elimination reaction to obtain diimino succinonitrile. In the present invention, the molar ratio of diaminomaleonitrile to 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is preferably 1: 1.1 to 1.5, more preferably 1: 1. In the present invention, the organic solvent preferably includes acetonitrile; in the present invention, the amount of the organic solvent used is not particularly limited, and it is sufficient to ensure that the elimination reaction proceeds smoothly. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the mixing order is preferably to dissolve diaminomaleonitrile in an organic solvent, add 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, and mix. In the invention, the temperature of the elimination reaction is preferably 10-50 ℃, more preferably room temperature, and the time of the elimination reaction is preferably 10-60 min, more preferably 15-30 min; the reaction occurring during the elimination reaction is represented by the formula (1):
after the elimination reaction, the present invention preferably further comprises a post-treatment comprising: and carrying out solid-liquid separation on the reaction liquid obtained by the elimination reaction, concentrating the obtained liquid product, and drying to obtain the diimino succinonitrile. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be used. The concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be used. The temperature and time for drying are not particularly limited in the present invention, and drying to constant weight may be carried out at a drying temperature well known to those skilled in the art.
After the diimino butanedinitrile is obtained, the diimino butanedinitrile, halogenated diaminopyridine and trifluoroacetic acid are mixed for cyclization reaction to obtain the halogenated pyridodicyanopyrazine.
In the invention, the molar ratio of the diimino butanedinitrile to the halogenated diaminopyridine is preferably 1 to 1.5: 1, more preferably 1.1 to 1.4: 1, more preferably 1.2 to 1.3: 1. in the present invention, the ratio of the amount of the diimino succinonitrile substance to the volume of trifluoroacetic acid (TFA) is preferably 0.1 to 0.5 mol: 1L, more preferably 0.15 to 0.4 mol: 1L, more preferably 0.15 to 0.2 mol: 1L of the compound. The mixing mode of the invention is not particularly limited, and the mixing mode known to those skilled in the art can be adopted, such as stirring and mixing; the mixing sequence is preferably that the diimino butanedinitrile and the halogenated diaminopyridine are mixed and then added into the trifluoroacetic acid in batches for mixing; the batch adding is preferably carried out for 2-3 times. In the invention, the temperature of the cyclization reaction is preferably 10-40 ℃, more preferably room temperature, and the time of the cyclization reaction is preferably 2-20 h, more preferably 4-10 h, and further preferably 8 h; the reaction occurring during the cyclization reaction is as shown in formula (2):
after the cyclization reaction, the present invention preferably further comprises a post-treatment comprising: and adding ice water into the reaction liquid obtained by the cyclization reaction, carrying out solid-liquid separation, washing the obtained solid product, and purifying to obtain the halogenated pyridodicyanopyrazine. The adding amount of the ice water is not particularly limited until the water phase is neutral. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be used. The concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be used. In the present invention, the purification is preferably silica gel column chromatography purification, and the eluent for silica gel column chromatography purification preferably comprises a large polar solvent-small polar solvent mixed solvent; the large polar solvent preferably comprises one or more of dichloromethane, ethyl acetate and acetone; the low-polarity solvent preferably comprises one or more of petroleum ether, diethyl ether and n-hexane; the volume ratio of the large polar solvent to the small polar solvent in the mixed solvent is preferably 1: 0.5 to 2, more preferably 1:1 to 1.5.
After obtaining the halogenated pyridodicyanopyrazine, mixing the halogenated pyridodicyanopyrazine, a compound II, a palladium catalyst and an alkaline reagent under a protective atmosphere, and carrying out a coupling reaction to obtain the pyridopyrazine compound with the structure shown in the formula I.
In the invention, the structural formula of the compound II is
In the compound II R1And R2The optional substituents of (A) are preferably as defined for R in said formula I1And R2The optional substituents are of the same kind and are not described in detail herein.
In the present invention, the molar ratio of the halopyridodicyanopyrazine to the compound II is preferably 1: 1.1 to 3, more preferably 1: 1.5 to 2.5, and more preferably 1: 2.
In the present invention, the alkaline agent preferably includes a carbonate and/or a bicarbonate, more preferably includes potassium carbonate and/or cesium carbonate. In the present invention, the molar ratio of the halopyridodicyanopyrazine to the basic agent is preferably 1: 4-10, more preferably 1: 4-8, and more preferably 1: 5 to 6.
In the present invention, the palladium catalyst preferably comprises tetrakis (triphenylphosphine) palladium and/or tris (dibenzylideneacetone) dipalladium, more preferably tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium. In the present invention, the molar ratio of the halopyridodicyanopyrazine to the palladium catalyst is preferably 1: 0.03 to 0.1, more preferably 1: 0.04 to 0.09, and more preferably 1: 0.05 to 0.08.
The protective atmosphere in the present invention is not particularly limited, and those known to those skilled in the art can be used, such as nitrogen, argon or helium.
The mixing method of the present invention is not particularly limited, and the mixing method known to those skilled in the art may be adopted, specifically, stirring and mixing.
In the present invention, the coupling reaction is preferably carried out in the presence of a solvent, which preferably comprises an organic solvent or an organic solvent-a water mixed solvent, the organic solvent and the organic solvent in the mixed solvent independently preferably comprise one or more of tetrahydrofuran, toluene, xylene, dioxane and N, N-dimethylformamide; in the mixed solvent, the volume ratio of the organic solvent to water is preferably 1: 0.1 to 0.5, more preferably 1: 0.2 to 0.4; the dosage of the solvent is not specially limited, and the coupling reaction can be ensured to be smoothly carried out. In the present invention, when the compound II is
When the solvent is used, the solvent is preferably an organic solvent-water mixed solvent; when the compound II is
When used, the solvent is preferably an organic solvent.
In the present invention, when the compound II is
When the coupling reaction is carried out in the presence of tri-tert-butylphosphine, the molar ratio of the halopyridodicyanopyrazine to the tri-tert-butylphosphine is preferably 1: 0.03 to 0.1, more preferably 1: 0.04 to 0.09, and more preferably 1: 0.05 to 0.08; the coupling reaction is Buchwald-Hartwig coupling reaction. In the present invention, when the compound II is
The coupling reaction is particularly a Suzuki coupling reaction.
In the invention, the temperature of the coupling reaction is preferably 80-110 ℃, more preferably 80-100 ℃, and further preferably 90-100 ℃; the time of the coupling reaction is preferably 12-24 hours, more preferably 14-22 hours, and further preferably 15-20 hours. In the present invention, the reaction occurring during the coupling reaction is represented by the formula (3):
after the coupling reaction, the present invention preferably further comprises a post-treatment comprising: and (3) placing the reaction solution obtained by the coupling reaction in water, extracting by using an organic solvent, concentrating the obtained organic phase, and purifying to obtain the pyridopyrazine compound. The amount of water added in the present invention is not particularly limited, and the alkaline agent in the system can be dissolved. In the present invention, the organic solvent for organic solvent extraction preferably includes one or more of dichloromethane, ethyl acetate and diethyl ether. The concentration method of the present invention is not particularly limited, and a concentration method known to those skilled in the art may be used. In the present invention, the purification is preferably silica gel column chromatography purification, and the eluent for silica gel column chromatography purification preferably comprises a large polar solvent-small polar solvent mixed solvent; the highly polar solvent preferably comprises dichloromethane, ethyl acetate and/or acetone; the low-polarity solvent preferably comprises one or more of petroleum ether, diethyl ether and n-hexane; the volume ratio of the large polar solvent to the small polar solvent in the mixed solvent is preferably 1: 1-4, more preferably 1: 1.5 to 3.
The invention provides application of the pyridopyrazine compound in the technical scheme or the pyridopyrazine compound obtained by the preparation method in the technical scheme in an organic electroluminescent device. In the present invention, the organic electroluminescent device preferably includes a yellow electroluminescent device, an orange electroluminescent device, a red electroluminescent device, or a near-infrared electroluminescent device. In the invention, the pyridopyrazine compound is preferably used as a non-doped luminescent layer material of an orange light electroluminescent device, a red light electroluminescent device or a near infrared light electroluminescent device, or is used as an object doped material of a doped luminescent layer of a yellow light electroluminescent device, an orange light electroluminescent device, a red light electroluminescent device or a near infrared light electroluminescent device.
The invention provides an organic electroluminescent device which comprises a light-emitting layer, an electrode layer and a functional layer, wherein the raw materials for preparing the light-emitting layer comprise the pyridopyrazine compound in the technical scheme or the pyridopyrazine compound obtained by the preparation method in the technical scheme.
In the present invention, the raw material for preparing the light-emitting layer preferably further includes a host material; the host material preferably comprises a small molecule host material and/or a high molecule host material; the small molecule host material preferably comprises one or more of 4,4 '-N, N' -dicarbazole biphenyl (CBP), 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 1,3, 5-tris (2-N-phenylbenzimidazolyl) benzene (TPBI), and 3- (4-diphenyl) -5- (4-tert-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-Triazole (TAZ); the polymer main body material comprises one or more of polystyrene, polyphenylene, polyvinylcarbazole, polycarbazole and polyfluorene; the host material of the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the invention, the mass ratio of the pyridopyrazine compound to the main material is preferably 1-30: 100, more preferably 5-25: 100, and even more preferably 10-20: 100. In the invention, the number of the luminescent layers is preferably not less than 1, and more preferably 1; the thickness of each light-emitting layer is preferably 40 to 50nm, more preferably 42 to 48nm, and further preferably 45 to 46 nm.
In the present invention, the electrode layer preferably includes an anode layer and a cathode layer; the anode layer preferably comprises an anode transparent conductive film shielding glass (ITO) layer; the thickness of the anode layer is preferably 10-60 nm, and more preferably 30-40 nm; the cathode layer preferably comprises an aluminium layer; the thickness of the cathode layer is preferably 1-4 nm, and more preferably 2-3 nm.
In the present invention, the organic electroluminescent device preferably further comprises a functional layer. In the present invention, the functional layer preferably includes one or more layers of a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and more preferably includes a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a hole transport layer and an electron injection layer; the hole transport layer is preferably disposed between the anode layer and the light emitting layer, and the electron transport layer and the electron injection layer are preferably disposed between the light emitting layer and the cathode layer. In the present invention, the raw materials for the preparation of the hole transport layer preferably include N, N '-bis (1-naphthyl) -N, N' -diphenyl-1, 1-biphenyl-4, 4 '-diamine, poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT/PSS), 4,4,4, -tris (carbazol-9-yl) triphenylamine, 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ], 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole; the thickness of the hole transport layer is preferably 10-60 nm, and more preferably 40 nm. In the present invention, the hole blocking layer is preferably prepared from a starting material comprising 4,4', 4 ″ -tris (9-carbazolyl) triphenylamine, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene; the thickness of the hole blocking layer is preferably 5-20 nm, and more preferably 10-15 nm. In the present invention, the raw materials for preparing the electron transport layer preferably include m-tris (phenylbenzimidazole) benzene (TPBI), 4, 7-diphenyl-1, 10-phenanthroline, 3- (4-diphenyl) -5- (4-tert-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-triazole; the thickness of the electron transport layer is preferably 10-40 nm, and more preferably 20-30 nm. In the present invention, the raw material for preparing the electron injection layer preferably includes LiF; the thickness of the electron injection layer is preferably 90-200 nm, and more preferably 150 nm.
In the present invention, the organic electroluminescent device preferably includes an anode layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, or an anode layer, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode layer, which are sequentially stacked.
The invention also provides a preparation method of the organic electroluminescent device in the technical scheme, which comprises the following steps:
preparing a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the surface of the anode layer in sequence to obtain an organic electroluminescent device; or, a hole transport layer, a light emitting layer, an electron injection layer and a cathode layer are sequentially prepared on the surface of the anode layer. In the invention, the preparation mode is preferably evaporation or solution coating; the electron injection layer and the cathode layer are more preferably prepared by plating. In the invention, the plating is preferably vacuum plating, and the vacuum degree of the vacuum plating is excellentIs selected to be 0.6 multiplied by 10-5～1.3×10-5Torr, more preferably 1X 10-5～1.1×10-5Torr). In the present invention, the solution for solution coating preferably includes a light emitting layer preparation raw material solution and a functional layer preparation raw material solution; the solvent in the luminescent layer preparation raw material solution preferably comprises one or more of toluene, xylene and chlorobenzene, and the concentration of the luminescent layer preparation raw material solution is preferably 0.5-2 g/L, more preferably 0.7-1.5 g/L, and further preferably 0.8-1 g/L; the solvent in the raw material solution for preparing the functional layer preferably comprises water, and the solid content of the raw material solution for preparing the functional layer is preferably 5-6%, more preferably 5.2-5.8%, and further preferably 5.4-5.6%.
The invention also provides the application of the organic electroluminescent device in the technical scheme in a lighting source, a signal lamp, an indication board or a flat panel display.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Synthesis of diimino succinonitrile
To 10mmol of diaminomaleonitrile, 50mL of acetonitrile was added, after stirring and dissolution, 10mmol of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone was added, after stirring for 15min, filtration was performed, and the obtained liquid fraction was concentrated and dried to constant weight to obtain diiminosuccinonitrile (brown solid, 1.01g, yield 95%).
(2) Synthesis of Compound 5, 8-dibromopyrido [3,4-b ] -2, 3-dicyanopyrazine (5,8-DBrPPD)
Mixing 3.6mmol of diimino butanedinitrile and 3mmol of 2, 5-dibromo-3, 4-diaminopyridine, adding the mixture into 20mL of trifluoroacetic acid in 3 batches, stirring at room temperature for 8h, pouring the mixture into ice water, filtering, washing the obtained solid component with water, and purifying by silica gel column chromatography (the eluent is petroleum ether/dichloromethane volume ratio is 1/1) to obtain 5, 8-dibromopyrido [3,4-b ] to obtain the 5, 8-dibromopyridine [3,4-b ] of]-2, 3-dicyanopyrazine (pale yellow powder, 2.71g, yield 80%). Structural characterization data:1H NMR(400MHz,CDCl3) δ 8.54(s, 1H); the mass of the molecular ions determined by mass spectrometry was: 338.86 (calculated value: 338.95); theoretical element content (%) C9HN5Br2: c31.8, H0.30, N20.66 and Br47.15; measured elemental content (%): c31.77, H0.35 and N20.49.
(3) Synthesis of Compound 5-bromopyrido [3,4-b ] -2, 3-dicyanopyrazine (5-BrPPD)
Preparation of 5-bromopyrido [3,4-b ] according to the procedure of step (2)]-2, 3-dicyanopyrazine, distinguished from step (2) by the substitution of 2, 5-dibromo-3, 4-diaminopyridine with 2-bromo-3, 4-diaminopyridine, giving 5-bromopyrido [3,4-b ]]-2, 3-dicyanopyrazine (pale yellow powder, 2.16g, 83% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.42(d, J ═ 6.8Hz,1H),7.78(d, J ═ 7.0Hz, 1H); the mass of the molecular ions determined by mass spectrometry was: 260.15 (calculated value: 258.95); theoretical element content (%) C9H2N5Br: c41.57, H0.78, N26.93, Br 30.73; measured elemental content (%): c41.69, H0.83 and N26.98.
(4) Synthesis of Compound 8-bromopyrido [3,4-b ] -2, 3-dicyanopyrazine (8-BrPPD)
Preparation of 8-bromopyrido [3,4-b ] according to the procedure of step (2)]-2, 3-dicyanopyrazine, distinguished from step (2) by the substitution of 2, 5-dibromo-3, 4-diaminopyridine with 3, 4-diamino-5-bromopyridine to give 8-bromopyrido [3,4-b ]]-2, 3-dicyanopyrazine (pale yellow powder, 1.95g, 75% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.77(s,1H),8.49(s, 1H); the mass of the molecular ions determined by mass spectrometry was: 260.15 (calculated value: 258.95); theoretical element content (%) C9H2N5Br: c41.57, H0.78, N26.93, Br 30.73; measured elemental content (%): c41.52, H0.84 and N26.71.
Example 2
3mmol of 5, 8-dbrpd prepared in example 1, 6.6mmol of 4-triphenylamine borate, 15mmol of potassium carbonate, 0.1mmol of tetrakis (triphenylphosphine) palladium, 45mL of toluene and 7.5mL of water were put into a three-necked flask, reacted for 12 hours under nitrogen protection, oil bath and 100 ℃, the obtained reaction liquid was poured into distilled water, extracted with dichloromethane, and the obtained organic phase was concentrated and purified by silica gel column chromatography (eluent petroleum ether/dichloromethane volume ratio: 1/3) to obtain pyridopyrazine compound (I-1, dark red powder, 1.60g, yield 80%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.90(s,1H),8.12(d, J ═ 7.2Hz,2H),7.55(d, J ═ 8.2Hz,2H),7.37(d, J ═ 8.4Hz,4H),7.26 to 7.22(m,8H),7.10 to 7.06(m,8H),7.02 to 6.98(m, 8H); the mass of the molecular ions determined by mass spectrometry was: 667.25 (calculated value: 667.78); theoretical element content (%) C45H29N7: c80.94, H4.38, N14.68; measured elemental content (%): c80.41, H4.52 and N15.07. The compound emits red light, the light-emitting wavelength is 660nm, and the fluorescence quantum yield is 9.2%.
Example 3
3mmol of 5,8-DBrPPD prepared in example 1, 6.6mmol of diphenylamine, 24mmol of cesium carbonate, 0.15mmol of tris (dibenzylideneacetone) dipalladium, 0.15mmol of tri-tert-butylphosphine and 80mL of o-xylene are added into a three-neck flask, reacted for 24 hours under the conditions of nitrogen protection, oil bath and 100 ℃, and the obtained reaction solution is poured into a flaskThe resulting organic phase was concentrated and purified by silica gel column chromatography (eluent petroleum ether/dichloromethane ratio by volume: 1/3) to obtain pyridopyrazines (I-2, 1.60g, 80% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.26-7.22(m,8H),7.17(s,1H),7.10-7.06(m,8H),7.02-6.98(m, 4H); the mass of the molecular ions determined by mass spectrometry was: 515.19 (calculated value: 515.58); theoretical element content (%) C33H21N7: c76.88, H4.11, N19.02; measured elemental content (%): c76.41, H4.52 and N19.07. The compound emits orange red light, the light-emitting wavelength is 610nm, and the fluorescence quantum yield is 11.3%.
Example 4
3mmol of 5-BrPPD prepared in example 1, 3.3mmol of 4-triphenylamine borate, 7.5mmol of potassium carbonate, 0.05mmol of tetrakis (triphenylphosphine) palladium, 25mL of toluene and 4mL of water () were put into a three-necked flask, reacted at 100 ℃ for 12 hours under nitrogen protection, in an oil bath, and the resulting reaction solution was poured into distilled water, extracted with dichloromethane, and the resulting organic phase was concentrated and purified by silica gel column chromatography (eluent petroleum ether/dichloromethane volume ratio: 2/3) to obtain pyridopyrazines (I-3, orange-red powder, 1.08g, yield 85%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.37(d, J ═ 6.8Hz,1H),8.12(d, J ═ 8.4Hz,2H),7.37(d, J ═ 8.4Hz,2H),7.26-7.22(m,4H),7.19(d, J ═ 7.0Hz,1H)7.10-7.06(m,4H),7.02-6.98(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 424.14 (calculated value: 424.47); theoretical element content (%) C27H16N6: c76.40, H3.80, N19.80; measured elemental content (%): c76.02, H3.92 and N20.06. The compound emits red light, the light-emitting wavelength is 640nm, and the fluorescence quantum yield is 10.2%.
Example 5
Adding 3mmol of 5-BrPPD prepared in example 1, 3.3mmol of diphenylamine, 12mmol of cesium carbonate, 0.08mmol of tris (dibenzylideneacetone) dipalladium, 0.08mmol of tri-tert-butylphosphine and 40mL of o-xylene into a three-neck flask, reacting for 24h under the conditions of nitrogen protection, oil bath and 100 ℃, pouring the obtained reaction solution into distilled water,dichloromethane extraction, concentration of the organic phase obtained and purification by column chromatography on silica gel (eluent: petroleum ether/dichloromethane volume ratio: 2/3) gave pyridopyrazine compound, I-4, as red powder, 0.87g, 83% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.92(d, J ═ 6.8Hz,1H),7.26-2.22(m,4H),7.10-7.06(m,4H),7.02-6.98(m,2H),6.81(d, J ═ 7.0Hz, 1H); the mass of the molecular ions determined by mass spectrometry was: 348.11 (calculated value: 348.37); theoretical element content (%) C33H21N7: c72.40, H3.47, N24.12; measured elemental content (%): c72.41, H3.50 and N24.09. The compound emits orange red light, the light-emitting wavelength is 590nm, and the fluorescence quantum yield is 9.5%.
Example 6
3mmol of 8-BrPPD prepared in example 1, 3.3mmol of 4-triphenylamine borate, 7.5mmol of potassium carbonate, 0.05mmol of tetrakis (triphenylphosphine) palladium, 25mL of toluene and 4mL of water were put into a three-necked flask, reacted for 12 hours under nitrogen protection, oil bath and 100 ℃, the obtained reaction solution was poured into distilled water, extracted with dichloromethane, and the obtained organic phase was concentrated and purified by silica gel column chromatography (eluent, petroleum ether/dichloromethane volume ratio: 1/2) to obtain pyridopyrazines (I-5, orange-red powder, 1.12g, yield 88%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 9.24(s,1H),8.69(s,1H),7.55(d, J ═ 8.4Hz,2H),7.37(d, J ═ 8.4Hz,2H),7.26-7.22(m,4H),7.10-7.06(m,4H),7.02-6.98(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 424.14 (calculated value: 424.47); theoretical element content (%) C27H16N6: c76.40, H3.80, N19.80; measured elemental content (%): c76.11, H3.96 and N19.93. The compound emits red light, the light-emitting wavelength is 650nm, and the fluorescence quantum yield is 8.5%.
Example 7
Adding 3mmol of 8-BrPPD prepared in example 1, 3.3mmol of diphenylamine, 12mmol of cesium carbonate, 0.08mmol of tris (dibenzylideneacetone) dipalladium, 0.08mmol of tri-tert-butylphosphine and 40mL of o-xylene into a three-neck bottle, and reacting for 24 hours at 100 ℃ in a nitrogen protection oil bath to obtain the productThe reaction mixture was poured into distilled water, extracted with dichloromethane, and the resulting organic phase was concentrated and purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane (vol): 1/2) to obtain pyridopyrazines (I-6, red powder, 0.84g, yield 80%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.23(s,1H),8.04(s,1H),7.26-2.22(m,4H),7.10-7.06(m,4H),7.02-6.98(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 348.11 (calculated value: 348.37); theoretical element content (%) C33H21N7: c72.40, H3.47, N24.12; measured elemental content (%): c72.21, H3.54, N24.25. The compound emits orange red light, the light-emitting wavelength is 570nm, and the fluorescence quantum yield is 6.8%.
Example 8
Prepared according to the preparation method of example 2, differing from example 2 in that 4- (4,4' -dimethylanilino) phenylboronic acid was used in place of 4-triphenylamine boronic acid, to give pyridopyrazines (I-7, dark red powder, 1.67g, 77% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.88(s,1H),8.10(d, J ═ 7.2Hz,2H),7.55(d, J ═ 8.2Hz,2H),7.37(d, J ═ 8.4Hz,4H),7.16-7.12(m,16H),2.32(s, 12H); the mass of the molecular ions determined by mass spectrometry was: 723.31 (calculated value: 723.88); theoretical element content (%) C49H37N7: c81.30, H5.15, N13.54; measured elemental content (%): c81.02, H5.18 and N13.80. The compound emits red light, the light-emitting wavelength is 625nm, and the fluorescence quantum yield is 10.0%.
Example 9
Pyridopyrazines were prepared according to the preparation method of example 3, differing from example 3 in that 4,4' -dimethyldiphenylamine was used instead of diphenylamine, to give pyridopyrazines (I-8, dark red powder, 1.41g, 82% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.17(s,1H),7.16-7.12(m,16H),2.32(s, 12H); the mass of the molecular ions determined by mass spectrometry was: 571.25 (calculated value: 571.69); theoretical element content (%) C37H29N7：C 77.74、H5.11, N17.15; measured elemental content (%): c77.51, H5.18 and N17.31. The compound emits orange red light, the light-emitting wavelength is 595nm, and the fluorescence quantum yield is 9.1%.
Example 10
Pyridopyrazine compound was prepared according to the preparation method of example 4, except that 4- (4,4' -dimethylanilino) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 4 to obtain pyridopyrazine compound (I-9, dark red powder, 1.10g, yield 81%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.37(d, J ═ 7.2Hz,1H),8.12(d, J ═ 8.4Hz,2H),7.37(d, J ═ 8.4Hz,2H),7.18(d, J ═ 7.0Hz,1H),7.16-7.12(m,8H),2.32(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 452.17 (calculated value: 452.52); theoretical element content (%) C29H20N6: c76.97, H4.46, N18.57; measured elemental content (%): c76.59, H4.61 and N18.80. The compound emits red light, the light-emitting wavelength is 645nm, and the fluorescence quantum yield is 9.2%.
Example 11
Pyridopyrazines were prepared according to the preparation method of example 5, differing from example 5 in that 4,4' -dimethyldiphenylamine was used instead of diphenylamine, to give pyridopyrazines (I-10, dark red powder, 0.95g, 84% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.92(d, J ═ 6.8Hz,1H),7.15-7.12(m,8H),6.81(d, J ═ 6.8Hz,1H),2.32(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 376.14 (calculated value: 376.42); theoretical element content (%) C23H16N6: c73.39, H4.28, N22.33; measured elemental content (%): c73.05, H4.41, N22.54. The compound emits orange red light, the light-emitting wavelength is 595nm, and the fluorescence quantum yield is 8.8%.
Example 12
A pyridopyrazine compound was prepared according to the preparation method of example 6, except that 4- (4,4' -dimethylanilino) phenylboronic acid was used in place of 4-triphenylamine boronic acid in example 6 to give a pyridopyrazine compound (I-11, orange-red powder, 1.11g, yield 82%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 9.24(s,1H),8.69(s,1H),7.57(d, J ═ 8.4Hz,2H),7.35(d, J ═ 8.4Hz,2H),7.16-2.12(m,8H),2.32(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 452.17 (calculated value: 452.52); theoretical element content (%) C29H20N6: c76.97, H4.46, N18.57; measured elemental content (%): c76.61, H4.63 and N18.76. The compound emits red light, the light-emitting wavelength is 645nm, and the fluorescence quantum yield is 8.8%.
Example 13
Pyridopyrazines were prepared according to the preparation method of example 7, differing from example 7 in that 4,4' -dimethyldiphenylamine was used instead of diphenylamine, to give pyridopyrazines (I-12, orange-red powder, 0.95g, 84% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.23(s,1H),8.04(s,1H),7.16-7.13(m,8H),2.32(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 376.14 (calculated value: 376.42); theoretical element content (%) C23H16N6: c73.39, H4.28, N22.33; measured elemental content (%): c73.11, H4.42 and N22.47. The compound emits orange red light, the light-emitting wavelength is 590nm, and the fluorescence quantum yield is 7.9%.
Example 14
Pyridopyrazine compound was prepared according to the preparation method of example 2, except that 4- (N-carbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 2 to obtain pyridopyrazine compound (I-13, dark red powder, 1.67g, 75% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.90(s,1H),7.98-7.93(m,6H),7.41(d, J ═ 8.2Hz,2H),6.92(d, J ═ 8.4Hz,4H),6.44-6.41(m,8H),5.80-5.78(m, 4H); the mass of the molecular ions determined by mass spectrometry was: 667.25 (calculated value: 667.78); theoretical element content (%) C45H29N7: c80.94, H4.38, N14.68; measured elemental content (%): c80.77, H4.49, N14.74. The compound emits red light, the light-emitting wavelength is 600nm, and the fluorescence quantum yield is 19.8%.
Example 15
Pyridopyrazines were prepared according to the preparation method of example 3, differing from example 3 in that diphenylamine was replaced with carbazole to give pyridopyrazines (I-14, red powder, 1.41g, yield 80%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.95-7.93(m,4H),7.17(s,1H),6.44-6.41(m,8H),5.81-5.78(m, 4H); the mass of the molecular ions determined by mass spectrometry was: 515.19 (calculated value: 515.58); theoretical element content (%) C33H21N7: c76.88, H4.11, N19.02; measured elemental content (%): c76.52, H4.18 and N19.30. The compound emits orange red light, the light-emitting wavelength is 575nm, and the fluorescence quantum yield is 14.2%.
Example 16
Pyridopyrazine compound was prepared according to the preparation method of example 4, except that 4- (N-carbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 4 to obtain pyridopyrazine compound (I-15, red powder, 1.10g, 83% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.37(d, J ═ 7.2Hz,1H),7.98-7.93(m,4H),7.18(d, J ═ 7.0Hz,1H),6.92(d, J ═ 8.2Hz,2H),6.44-6.41(m,4H),5.79-5.76(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 424.14 (calculated value: 424.47); theoretical element content (%) C27H16N6: c76.40, H3.80, N19.80; measured elemental content (%): c76.51, H3.91, N19.58. The compound emits red light, the light-emitting wavelength is 605nm, and the fluorescence quantum yield is 15.1%.
Example 17
Pyridopyrazines were prepared according to the preparation method of example 5, differing from example 5 in that diphenylamine was replaced with carbazole to give pyridopyrazines (I-16, red powder, 1.41g, yield 80%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.94-7.92(m,3H),6.81(d, J ═ 6.8Hz,1H),6.44-6.41(m,4H),5.79-5.77(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 348.11 (calculated value: 348.37); theoretical element content (%) C21H12N6: c72.40, H3.47, N24.12; measured elemental content (%): c72.21, H3.51, N24.28. The compound emits orange red light, the light-emitting wavelength is 570nm, and the fluorescence quantum yield is 12.0%.
Example 18
Pyridopyrazines were prepared according to the preparation method of example 6, except that 4- (N-carbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 6, to give pyridopyrazines (I-17, orange-red powder, 1.02g, 80% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 9.24(s,1H),8.69(s,1H),7.96-7.93(m,2H),7.41(d, J ═ 8.4Hz,2H),6.92(d, J ═ 8.2Hz,2H),6.44-6.41(m,4H),5.79-5.76(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 424.14 (calculated value: 424.47); theoretical element content (%) C27H16N6: c76.40, H3.80, N19.80; measured elemental content (%): c76.29, H3.89 and N19.82. The compound emits red light, the light-emitting wavelength is 605nm, and the fluorescence quantum yield is 13.3%.
Example 19
Pyridopyrazines were prepared according to the preparation method of example 7, except that diphenylamine was replaced with carbazole in place of example 7, to give pyridopyrazines (I-18, orange-red powder, 0.81g, 77% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.23(s,1H),8.04(s,1H),7.94-7.92(m,2H),6.81(d, J ═ 6.8Hz,1H),6.44-6.41(m,4H),5.79-5.77(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 348.11 (calculated value: 348.37); theoretical element content (%) C21H12N6: c72.40, H3.47, N24.12; measured elemental content (%): c72.17, H3.53, N24.30. The compound emits orange red light, the light-emitting wavelength is 575nm, and the fluorescence quantum yield is 10.0%.
Example 20
A pyridopyrazine compound was prepared according to the preparation method of example 2, differing from example 2 in that 4- (N-3, 6-di-tert-butylcarbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid, to give a pyridopyrazine compound (I-19, deep red powder,2.09g, 78% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.90(s,1H),7.98(d, J ═ 8.4Hz,2H),7.41(d, J ═ 8.2Hz,2H),6.92(d, J ═ 8.4Hz,4H),6.43-6.41(m,4H),6.22(s,4H),5.80-5.78(m,4H),1.34(s, 36H); the mass of the molecular ions determined by mass spectrometry was: 891.50 (calculated value: 892.21); theoretical element content (%) C61H61N7: c82.12, H6.89, N10.99; measured elemental content (%): c81.91, H6.93 and N11.16. The compound emits red light, the light-emitting wavelength is 650nm, and the fluorescence quantum yield is 14.8%.
Example 21
Pyridopyrazines were prepared according to the preparation method of example 3, differing from example 3 in that diphenylamine was replaced with 3, 6-di-tert-butylcarbazole, to give pyridopyrazines (I-20, orange-red powder, 1.69g, 76% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.17(s,1H),6.44-6.41(m,4H),6.22(s,4H),5.81-5.78(m,4H),1.34(s, 36H); the mass of the molecular ions determined by mass spectrometry was: 739.44 (calculated value: 740.01); theoretical element content (%) C49H53N7: c79.53, H7.22, N13.25; measured elemental content (%): c79.28, H7.32 and N13.40. The compound emits orange red light, the light-emitting wavelength is 580nm, and the fluorescence quantum yield is 11.3%.
Example 22
Pyridopyrazine compound was prepared according to the preparation method of example 4, except that 4- (N-3, 6-di-tert-butylcarbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 4 to obtain pyridopyrazine compound (I-21, red powder, 1.34g, yield 83%). Structural characterization data:1HNMR(400MHz,DMSO-d6) δ 8.37(d, J ═ 7.2Hz,1H),7.98(m, J ═ 8.4Hz,2H),7.18(d, J ═ 7.0Hz,1H),6.92(d, J ═ 8.4Hz,2H),6.44-6.41(m,2H),6.22(s,2H),5.79-5.76(m,2H),1.34(s, 18H); the mass of the molecular ions determined by mass spectrometry was: 536.27 (calculated value: 536.68); theoretical element content (%) C35H32N6: c78.33, H6.01, N15.66; measured elemental content (%): c78.19, H6.05 and N15.76.The compound emits red light, the light-emitting wavelength is 645nm, and the fluorescence quantum yield is 12.0%.
Example 23
Pyridopyrazines were prepared according to the preparation method of example 5, differing from example 5 in that diphenylamine was replaced with carbazole to give pyridopyrazines (I-22, red powder, 1.41g, yield 80%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.92(d, J ═ 6.8Hz,1H),6.81(d, J ═ 6.8Hz,1H),6.44-6.41(m,4H),6.22(s,2H),1.34(s, 18H); the mass of the molecular ions determined by mass spectrometry was: 460.24 (calculated value: 460.59); theoretical element content (%) C29H28N6: c75.63, H6.13, N18.25; measured elemental content (%): c75.31, H6.17, N18.52. The compound emits orange red light, the light-emitting wavelength is 575nm, and the fluorescence quantum yield is 9.6%.
Example 24
Pyridopyrazine compound was prepared according to the preparation method of example 6, except that 4- (N-3, 6-di-tert-butylcarbazolyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 6 to obtain pyridopyrazine compound (I-23, orange-red powder, 1.02g, 83% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 9.23(s,1H),8.68(s,1H),7.41(d, J ═ 8.4Hz,2H),6.92(d, J ═ 8.2Hz,2H),6.44-6.41(m,2H),6.12(s,2H),5.79-5.77(m,2H),1.34(s, 18H); the mass of the molecular ions determined by mass spectrometry was: 536.27 (calculated value: 536.68); theoretical element content (%) C35H32N6: c78.33, H6.01, N15.66; measured elemental content (%): c78.20, H6.14, N15.66. The compound emits red light, the light-emitting wavelength is 640nm, and the fluorescence quantum yield is 10.5%.
Example 25
Pyridopyrazines were prepared according to the preparation method of example 7, except that 3, 6-di-tert-butylcarbazole was used instead of diphenylamine in place of example 7 to give pyridopyrazines (I-24, orange-red powder, 1.04g, 75% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6)δ8.24(s,1H),8.03(s1H),6.43-6.40(m,2H),6.12(s,2H),5.78-5.76(m,2H),1.34(s, 18H); the mass of the molecular ions determined by mass spectrometry was: 460.24 (calculated value: 460.59); theoretical element content (%) C29H28N6: c75.63, H6.13, N18.25; measured elemental content (%): c75.29, H6.19, N18.52. The compound emits orange red light, the light-emitting wavelength is 570nm, and the fluorescence quantum yield is 7.9%.
Example 26
A pyridopyrazine compound was prepared according to the preparation method of example 2, differing from example 2 in that 4- (N-9, 9-dimethylazazinyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid, to give a pyridopyrazine compound (I-25, dark red powder, 2.09g, 73% yield). Structural characterization data:1HNMR(400MHz,DMSO-d6) δ 8.90(s,1H),8.12(d, J ═ 8.4Hz,2H),7.55(d, J ═ 8.2Hz,2H),7.37(d, J ═ 8.4Hz,4H),7.19-7.14(m,12H),6.96-6.93(m,4H),1.69(s, 12H); the mass of the molecular ions determined by mass spectrometry was: 747.31 (calculated value: 747.91); theoretical element content (%) C51H37N7: c81.90, H4.99, N13.11; measured elemental content (%): c81.91, H5.04 and N13.05. The material emits deep red light, the light-emitting wavelength is 700nm, and the fluorescence quantum yield is 6.9%.
Example 27
Pyridopyrazines were prepared according to the preparation method of example 3, except that 9, 9-dimethylacridine was used instead of diphenylamine, to give pyridopyrazines (I-26, orange-red powder, 1.43g, yield 80%) from example 3. Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.19-7.14(m,13H),6.97-6.94(m,4H),1.69(s, 12H); the mass of the molecular ions determined by mass spectrometry was: 595.25 (calculated value: 595.71); theoretical element content (%) C39H29N7: c78.63, H4.91, N16.46; measured elemental content (%): c78.25, H4.99 and N16.76. The compound emits red light, the light-emitting wavelength is 665nm, and the fluorescence quantum yield is 7.4%.
Example 28
Pyrido was prepared according to the preparation of example 4A pyrazine compound was obtained which was different from example 4 in that 4- (N-9, 9-dimethylazedinyl) phenylboronic acid was used in place of 4-triphenylamine boronic acid to give a pyridopyrazine compound (I-27, orange-red powder, 1.11g, yield 80%). Structural characterization data:1HNMR(400MHz,DMSO-d6) δ 8.37(d, J ═ 7.2Hz,1H),8.12(m, J ═ 8.4Hz,2H),7.37(d, J ═ 8.4Hz,2H),7.19-7.14(m,7H),6.98-6.94(m,2H),1.69(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 464.17 (calculated value: 464.53); theoretical element content (%) C30H20N6: c77.57, H4.34, N18.09; measured elemental content (%): c77.31, H4.46 and N18.23. The material emits deep red light, the light-emitting wavelength is 690nm, and the fluorescence quantum yield is 6.0%.
Example 29
Pyridopyrazines were prepared according to the preparation method of example 5, except that 9, 9-dimethylacridine was used instead of diphenylamine in place of example 5 to give pyridopyrazines (I-28, orange-red powder, 0.93g, 77% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.94(d, J ═ 6.8Hz,1H),7.19-7.14(m,6H),6.96-6.93(m,2H),6.81(d, J ═ 6.8Hz,1H),1.34(s, 18H); the mass of the molecular ions determined by mass spectrometry was: 388.14 (calculated value: 388.43); theoretical element content (%) C24H16N6: c74.21, H4.15, N21.64; measured elemental content (%): c74.02, H4.23, N21.75. The compound emits red light, the light-emitting wavelength is 670nm, and the fluorescence quantum yield is 6.9%.
Example 30
Pyridopyrazines were prepared according to the preparation method of example 6, except that 4- (N-9, 9-dimethylazedinyl) phenylboronic acid was used instead of 4-triphenylamine boronic acid in example 6 to give pyridopyrazines (I-29, orange-red powder, 1.11g, yield 80%). Structural characterization data:1HNMR(400MHz,DMSO-d6) δ 9.24(s,1H),8.69(s,1H),7.55(d, J ═ 8.4Hz,2H),7.37(d, J ═ 8.4Hz,2H),7.19-7.14(m,6H),6.95-6.92(m,2H),1.69(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 464.17 (calculated value: 464.53); theoretical element content(％)C30H20N6: c77.57, H4.34, N18.09; measured elemental content (%): c77.39, H4.46 and N18.15. The material emits deep red light, the light-emitting wavelength is 685nm, and the fluorescence quantum yield is 5.6%.
Example 31
Pyridopyrazines were prepared according to the preparation method of example 7, except that 9, 9-dimethylacridine was used instead of diphenylamine in place of example 7 to give pyridopyrazines (I-30, orange-red powder, 0.91g, 78% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.23(s,1H),8.04(s,1H),7.19-7.15(m,6H),6.95-6.92(m,2H),1.69(s, 6H); the mass of the molecular ions determined by mass spectrometry was: 388.14 (calculated value: 388.43); theoretical element content (%) C24H16N6: c74.21, H4.15, N21.64; measured elemental content (%): c73.99, H4.22, N21.79. The compound emits red light, the light-emitting wavelength is 665nm, and the fluorescence quantum yield is 5.8%.
Example 32
Pyridopyrazines were prepared according to the preparation method of example 3, differing from example 3 in that phenoxazine was used instead of diphenylamine, to give pyridopyrazines (I-31, red powder, 1.43g, 76% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.30-7.27(m,2H),7.17(s,1H),7.08-7.04(m,2H),6.89-6.85(m,4H),6.66-6.63(m,4H),5.83-5.79(m, 4H); the mass of the molecular ions determined by mass spectrometry was: 547.18 (calculated value: 547.58); theoretical element content (%) C33H21N7O2: c72.38, H3.87, N17.91; measured elemental content (%): c72.21, H3.95 and N23.84. The material emits near infrared light, the light-emitting wavelength is 710nm, and the fluorescence quantum yield is 5.7%.
Example 33
Pyridopyrazines were prepared according to the preparation method of example 5, differing from example 5 in that phenoxazine was used instead of diphenylamine, to give pyridopyrazines (I-32, orange-red powder, 0.82g, 75% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.92(d, J ═ 6.4Hz,1H),7.30-7.27(m,4H),6.89-6.81(m,3H),5.83-5.79(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 364.11 (calculated value: 364.37); theoretical element content (%) C21H12N6O: c69.22, H3.32, N23.07; measured elemental content (%): c69.01, H3.40, N27.21. The material emits deep red light, the light-emitting wavelength is 695nm, and the fluorescence quantum yield is 5.5%.
Example 34
Pyridopyrazines were prepared according to the preparation method of example 7, differing from example 7 in that phenoxazine was used instead of diphenylamine, to give pyridopyrazines (I-33, orange-red powder, 0.91g, 80% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.23(s,1H),8.04(s,1H),7.10-7.06(m,2H),6.89-6.84(m,4H),6.64-6.59(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 364.11 (calculated value: 364.37); theoretical element content (%) C21H12N6O: c69.22, H3.32, N23.07; measured elemental content (%): c69.33, H3.40, N27.00. The material emits deep red light, the light-emitting wavelength is 690nm, and the fluorescence quantum yield is 5.0%.
Example 35
A pyridopyrazine compound was prepared according to the preparation method of example 3, differing from example 3 in that diphenylamine was replaced with phenothiazine to obtain the pyridopyrazine compound (I-34, dark red powder, 1.43g, yield 75%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.30-7.27(m,4H),7.19-7.17(m,5H),7.08-7.04(m,4H),6.85-6.82(m, 4H); the mass of the molecular ions determined by mass spectrometry was: 579.13 (calculated value: 579.70); theoretical element content (%) C33H21N7O2: c68.37, H3.65, N16.91; measured elemental content (%): c68.08, H3.91 and N16.77. The material emits near infrared light, the light-emitting wavelength is 730nm, and the fluorescence quantum yield is 4.3%.
Example 36
Preparation of pyridopyrazines according to the preparation of example 5The compound was distinguished from example 5 in that phenothiazine was used in place of diphenylamine to give a pyridopyrazine (I-35, dark red powder, 0.80g, 73% yield). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 7.92(d, J ═ 6.4Hz,1H),7.31-7.27(m,4H),6.89-6.81(m,3H),5.80-5.74(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 364.11 (calculated value: 364.37); theoretical element content (%) C21H12N6S: c66.30, H3.18, N22.09; measured elemental content (%): c66.14, H3.30, N22.13. The material emits near infrared light, the light-emitting wavelength is 720nm, and the fluorescence quantum yield is 3.2%.
Example 37
A pyridopyrazine compound was prepared according to the preparation method of example 7, differing from example 7 in that diphenylamine was replaced with phenothiazine to obtain the pyridopyrazine compound (I-36, red powder, 0.90g, yield 82%). Structural characterization data:1H NMR(400MHz,DMSO-d6) δ 8.24(s,1H),8.05(s,1H),7.08-7.04(m,2H),6.84-6.80(m,4H),6.58-6.53(m, 2H); the mass of the molecular ions determined by mass spectrometry was: 364.11 (calculated value: 364.37); theoretical element content (%) C21H12N6S: c66.30, H3.18, N22.09; measured elemental content (%): c66.34, H3.29 and N22.21. The material emits near infrared light, the light-emitting wavelength is 715nm, and the fluorescence quantum yield is 3.0%.
Example 38
An organic electroluminescent device (marked as IT 0/NPB/TCTA/compound 1/TPBI/LiF/Al) is obtained by sequentially evaporating a hole transport layer NPB (thickness is 60nm), a hole blocking layer TCTA (thickness is 12nm), a light-emitting layer (the pyridopyrazine compound I-1 prepared in example 2, thickness is 20nm), an electron transport layer TPBI (thickness is 25nm), an electron injection layer LiF (thickness is 5nm) and an Al cathode layer (thickness is 200nm) on a glass substrate plated with an ITO anode. The starting voltage of the organic electroluminescent device is 3.9V, the maximum current efficiency is 1.31cd/A, and the power efficiency is 1.91 m/W; emitting deep red light with peak position of 690nm and maximum brightness of 1059cd/m2。
FIG. 1 is a photograph of a film prepared in example 38As can be seen from FIG. 1, the organic electroluminescent device emits deep red light with a peak of 690nm and a maximum luminance of 1059cd/m2。
Example 39
An organic electroluminescent device (marked as IT 0/NPB/TCTA/pyridopyrazine compound I-13/TPBI/LiF/Al) was obtained by sequentially evaporating a hole transport layer NPB (thickness 60nm), a hole blocking layer TCTA (thickness 12nm), a light-emitting layer (pyridopyrazine compound I-13 prepared in example 14, thickness 20nm), an electron transport layer TPBI (thickness 25nm), an electron injection layer LiF (thickness 5nm) and an Al cathode layer (thickness 200nm) on a glass substrate plated with an ITO anode. The starting voltage of the organic electroluminescent device is 3.0V, the maximum current efficiency is 3.80cd/A, and the power efficiency is 5.96 m/W; red light emission, peak position 600nm, maximum luminance 6680cd/m2。
FIG. 2 is a spectrum diagram of an organic electroluminescent device prepared in example 39, from FIG. 2, it can be seen that the organic electroluminescent device emits red light, has a peak position of 690nm and a maximum luminance of 6680cd/m2。
Example 40
An organic electroluminescent device (ITO/NPB/TCTA/pyridopyrazine compound I-19/TPBI/LiF/Al) was obtained by sequentially evaporating a hole transport layer NPB (thickness 60nm), a hole blocking layer TCTA (thickness 12nm), a light-emitting layer (pyridopyrazine compound I-19 prepared in example 20, thickness 20nm), an electron transport layer TPBI (thickness 25nm), an electron injection layer LiF (thickness 5nm), and an Al cathode layer (thickness 200nm) on a glass substrate coated with an ITO anode. The starting voltage of the organic electroluminescent device is 4.4V, the maximum current efficiency is 3.92cd/A, and the power efficiency is 7.44 m/W; red light emission, peak position 650nm, maximum luminance 3730cd/m2。
EXAMPLE 41
A hole transport layer NPB (thickness of 60nm), a hole blocking layer TCTA (thickness of 10nm), a light-emitting layer (20 wt% of TPBI doped with the pyridopyrazine compound I-1 prepared in example 2, thickness of 20nm), an electron transport layer TPBI (thickness of 30nm), and an electron injection layer LiF are sequentially evaporated on a glass substrate plated with an ITO anode(thickness of 5nm) and an Al cathode layer (thickness of 200nm) to obtain an organic electroluminescent device (marked as ITO/NPB/TCTA/TPBI: pyridopyrazine compound I-1(20 wt%)/TPBI/LiF/Al). The starting voltage of the organic electroluminescent device is 3.1V, the maximum current efficiency is 5.6cd/A, and the power efficiency is 5.1 lm/W; emitting deep red light with peak position of 668nm and maximum brightness of 3720cd/m2。
FIG. 3 is a spectrum diagram of an organic electroluminescent device prepared in example 41, from FIG. 3, it can be seen that the organic electroluminescent device emits deep red light with a peak position of 668nm and a maximum luminance of 3720cd/m2。
Example 42
An organic electroluminescent device (TO/NPB/TCTA/TPBI: pyridopyrazine compound I-13(20 wt%)/TPBI/LiF/Al) was obtained by sequentially evaporating a hole transport layer NPB (60 nm thick), a hole blocking layer TCTA (10 nm thick), a light-emitting layer (TPBI doped with 20 wt% of pyridopyrazine compound I-13 prepared in example 14, 20nm thick), an electron transport layer TPBI (30nm thick), an electron injection layer LiF (5nm) and an Al cathode layer (200 nm thick) on a glass substrate plated with an ITO anode. The starting voltage of the organic electroluminescent device is 3.1V, the maximum current efficiency is 25.1cd/A, and the power efficiency is 18.5 lm/W; emitting orange red light with peak position of 580nm and maximum brightness of 10700cd/m2。
FIG. 4 is a spectrum diagram of an organic electroluminescent device prepared in example 42, from FIG. 4, it can be seen that the organic electroluminescent device emits orange light, has a peak position of 580nm, and has a maximum luminance of 10700cd/m2。
Example 43
An organic electroluminescent device (marked as ITO/NPB/TCTA/TPBI: pyridopyrazine compound I-19(wt 20%)/TPBI/LiF/Al) was obtained by sequentially evaporating a hole transport layer NPB (thickness of 60nm), a hole blocking layer TCTA (thickness of 10nm), a light-emitting layer (20 nm thick TPBI doped with 20 wt% of pyridopyrazine compound I-19 prepared in example 20), an electron transport layer TPBI (30nm), an electron injection layer LiF (5nm) and an Al cathode layer (thickness of 200nm) on a glass substrate plated with an ITO anode. The organic electroluminescent device has a turn-on voltage of 3.1V and a maximum current efficiency of19.8cd/A, power efficiency 18.2 lm/W; red light emission, peak position 600nm, maximum luminance 8950cd/m2。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A pyridopyrazine compound, characterized by having the structure shown in formula I:
in the formula I, R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
2. Pyridopyrazines according to claim 1, wherein R is1And R2Independently comprises hydrogen and any one of the following structures:
3. a process for the preparation of pyridopyrazines according to any one of claims 1 to 2, comprising the steps of:
under a protective atmosphere, mixing the halogenated pyridodicyanopyrazine, a compound II, a palladium catalyst and an alkaline reagent, and carrying out a coupling reaction to obtain a pyridopyrazine compound with a structure shown in a formula I;
said halopyrido-diThe structure formula of the cyanopyrazine is
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time;
the structural formula of the compound II is
In the compound II R1And R2Independently comprises any one of hydrogen, triphenylamine substituent, diphenylamine substituent, carbazole substituent, N-phenylcarbazole substituent, phenoxazine substituent and phenothiazine substituent, and R is1And R2Not hydrogen at the same time.
4. A process according to claim 3, wherein said process for the preparation of halopyridodicyanopyrazines comprises the following steps:
mixing diimino butanedinitrile, halogenated diaminopyridine and trifluoroacetic acid, and carrying out cyclization reaction to obtain halogenated pyridodicyanopyrazine;
the structural formula of the halogenated diaminopyridine is shown in the specification
Wherein R is3And R4Independently is hydrogen, bromine or iodine, and R3And R4Not hydrogen at the same time.
5. The process according to claim 3 or 4, wherein the molar ratio between said halopyridodicyanopyrazine and compound II is 1: 1.1-3;
the molar ratio of the halogenated pyridodicyanopyrazine to the alkaline reagent is 1: 4-10;
the temperature of the coupling reaction is 80-110 ℃, and the time is 12-24 h.
6. Use of the pyridopyrazine compound according to any of claims 1 to 2 or the pyridopyrazine compound obtained by the preparation method according to any of claims 3 to 5 in organic electroluminescent devices.
7. An organic electroluminescent device, comprising a luminescent layer, an electrode layer and a functional layer, wherein the raw material for preparing the luminescent layer comprises the pyridopyrazine compound according to any of claims 1 to 2 or the pyridopyrazine compound obtained by the preparation method according to any of claims 3 to 5.
8. The organic electroluminescent device according to claim 7, wherein the raw material for producing the light-emitting layer further comprises a host material;
the host material comprises a small molecule host material and/or a high molecule host material;
the micromolecule main body material comprises one or more of 4,4 '-N, N' -dicarbazole biphenyl, 2- (4-diphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole, 1,3, 5-tri (2-N-phenyl benzimidazolyl) benzene and 3- (4-diphenyl) -5- (4-tert-butylphenyl) -4- (4-ethylphenyl) -,1,2, 4-triazole;
the polymer main body material comprises one or more of polystyrene, polyphenylene, polyvinyl carbazole, polycarbazole and polyfluorene.
9. The organic electroluminescent device according to claim 7 or 8, wherein the functional layer comprises one or more of a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
10. Use of the organic electroluminescent device as claimed in any one of claims 7 to 9 in an illumination source, a signal lamp, a sign or a flat panel display.
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