WO2020135790A1 - 一种含硼的化合物及其在有机电致发光器件上的应用 - Google Patents
一种含硼的化合物及其在有机电致发光器件上的应用 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 98
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000002346 layers by function Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 53
- -1 dibenzofuranyl Chemical group 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 20
- 125000005842 heteroatom Chemical group 0.000 claims description 20
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052805 deuterium Inorganic materials 0.000 claims description 14
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 12
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 12
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 12
- 229910052722 tritium Inorganic materials 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000004076 pyridyl group Chemical group 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 10
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 241000720974 Protium Species 0.000 claims description 6
- 150000001975 deuterium Chemical group 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical group FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CRXBTDWNHVBEIC-UHFFFAOYSA-N 1,2-dimethyl-9h-fluorene Chemical class C1=CC=C2CC3=C(C)C(C)=CC=C3C2=C1 CRXBTDWNHVBEIC-UHFFFAOYSA-N 0.000 claims description 2
- QTPLEVOKSWEYAC-UHFFFAOYSA-N 1,2-diphenyl-9h-fluorene Chemical class C=1C=CC=CC=1C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=CC=C1 QTPLEVOKSWEYAC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000005566 carbazolylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 150000003220 pyrenes Chemical class 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 claims description 2
- 125000006836 terphenylene group Chemical group 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims 1
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
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- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 20
- 238000001308 synthesis method Methods 0.000 description 19
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000903 blocking effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000005525 hole transport Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008204 material by function Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
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- 229910002027 silica gel Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *=Bc1cccc(B(c2cccc3c2[n]2-c4c5B6c7c2c3ccc7)c4ccc5-c2c6cccc2)c1 Chemical compound *=Bc1cccc(B(c2cccc3c2[n]2-c4c5B6c7c2c3ccc7)c4ccc5-c2c6cccc2)c1 0.000 description 1
- XUPGHXOMNMMNIA-UHFFFAOYSA-N Bc1ccc(C(c(c-2c3)cc4c3-c3ccccc3C4(C)C)(c3ccccc3)c3ccccc3)c-2c1 Chemical compound Bc1ccc(C(c(c-2c3)cc4c3-c3ccccc3C4(C)C)(c3ccccc3)c3ccccc3)c-2c1 XUPGHXOMNMMNIA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OTPVDTJVBHDVMO-UHFFFAOYSA-N CC1(C)c(cc(C(c(c-2c3)ccc3-c3cccc(B(c(cccc45)c4[n]4-c6c7B8c9c4c5ccc9)c6ccc7-c4c8cccc4)c3)(c3ccccc3)c3ccccc3)c-2c2)c2-c2c1cccc2 Chemical compound CC1(C)c(cc(C(c(c-2c3)ccc3-c3cccc(B(c(cccc45)c4[n]4-c6c7B8c9c4c5ccc9)c6ccc7-c4c8cccc4)c3)(c3ccccc3)c3ccccc3)c-2c2)c2-c2c1cccc2 OTPVDTJVBHDVMO-UHFFFAOYSA-N 0.000 description 1
- 108010024433 H 256 Proteins 0.000 description 1
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- RAHZBDMWVQIBRU-UHFFFAOYSA-N c1ccc(B(c2c3cccc2)c2cccc4c2B3c2cccc3c2N4c(cc(cc2)-c4ccc(c5ccccc5[s]5)c5c4)c2N3c2ccccc2)cc1 Chemical compound c1ccc(B(c2c3cccc2)c2cccc4c2B3c2cccc3c2N4c(cc(cc2)-c4ccc(c5ccccc5[s]5)c5c4)c2N3c2ccccc2)cc1 RAHZBDMWVQIBRU-UHFFFAOYSA-N 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
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- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the invention relates to the technical field of semiconductors, in particular to a boron-containing compound and its application in organic electroluminescent devices.
- OLED display technology has been applied in the fields of smartphones and tablets, and will be further expanded to large-scale applications such as TVs.
- the luminous efficiency of OLED devices, performance and other performance It needs further improvement.
- Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device.
- the continuous improvement of the performance of OLED devices not only the innovation of OLED device structure and manufacturing process, but also the continuous research and innovation of OLED photoelectric functional materials are needed to create functional materials of higher performance OLED.
- the OLED photoelectric functional materials used in OLED devices can be divided into two categories from the use, namely charge injection transport materials and luminescent materials. Further, charge injection transport materials can be divided into electron injection transport materials, electron blocking materials, holes Injection transport materials and hole blocking materials can also be divided into host luminescent materials and doped materials. In order to produce high-performance OLED light-emitting devices, various organic functional materials are required to have good photoelectric characteristics, for example, as charge transport materials, good carrier mobility, high glass transition temperature, etc. are required as the main body of the light-emitting layer Materials require materials with good bipolarity, appropriate HOMO/LUMO energy levels, etc.
- the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and electrons
- Various film layers such as transport layer and electron injection layer, that is to say, the photoelectric functional materials used in OLED devices include at least hole injection materials, hole transport materials, luminescent materials, electron transport materials, etc. Characteristics of sex and diversity.
- the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in devices with different structures may also be completely different.
- the present invention provides a boron-containing compound and its application in organic electroluminescent devices.
- the compound of the present invention contains a boron structure, has a high glass transition temperature and molecular thermal stability, and has suitable HOMO and LUMO energy levels. After being applied to an OLED device, it can effectively improve the luminous efficiency of the device and the service life of the OLED device.
- W 1 , W 2 , and W 3 each independently represent a nitrogen atom or a boron atom, and only one of W 1 , W 2 , and W 3 represents a nitrogen atom;
- a, b, c, d, and e are independently represented as 0 or 1, and a+b+c+d+e ⁇ 1;
- X 1 , X 2 , X 3 , X 4 and X 5 are independently represented as single bonds, sulfur atoms, oxygen atoms, N(R 6 ), B(R 7 ), C(R 8 )(R 9 ) or Si(R 10 )(R 11 ); where R 8 and R 9 , R 10 and R 11 are connected to form a ring or not Ring; at least one of X 1 , X 2 , X 3 , X 4 and X 5 is not represented as a single bond;
- L represents the same or differently means substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridinylene, substituted or unsubstituted Biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted carbazolylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted spirofluorenyl, substituted or Unsubstituted dimethylfluorene, substituted or unsubstituted diphenylfluorene;
- ⁇ , ⁇ , ⁇ , ⁇ , ⁇ are independently expressed as 1, 2 or 3;
- Y 1 to Y 21 each independently represent a nitrogen atom or CR or CLR 1 or CLR 2 or CLR 3 or CLR 4 or CLR 5 ;
- a , B, c, d, e are independently expressed as 1, when Y 21 , Y 1 , Y 16 , Y 17 , Y 13 , Y 14 , Y 8 , Y 9 , Y 4 , Y 5 are only represented as carbon atoms ,
- the rest can be independently expressed as nitrogen atom or CR or CLR 1 or CLR 2 or CLR 3 or CLR 4 or CLR 5 ;
- the R represents hydrogen atom, protium, deuterium, tritium, cyano group, halogen atom, C 1 -C 20 alkyl group, C 1 -C 20 alkyl substituted silane group, substituted or unsubstituted C 6 -C 20 One of aryl groups, substituted or unsubstituted heteroaryl groups containing one or more heteroatoms, C 6 -C 20 aryl groups or 5- to 30-membered heteroaryl substituted amine groups;
- R 1 to R 5 each independently represent a hydrogen atom, a protium atom, a deuterium atom, a tritium atom, a fluorine atom, a cyano group, C 1 -C 20 alkyl, C 1 -C 20 alkyl-substituted silyl group, a substituted or unsubstituted Among substituted C 6 -C 20 aryl groups, substituted or unsubstituted heteroaryl groups containing one or more heteroatoms, C 6 -C 20 aryl groups or 5- to 30-membered heteroaryl substituted amine groups
- a protium atom a deuterium atom, a tritium atom, a fluorine atom, a cyano group
- C 1 -C 20 alkyl C 1 -C 20 alkyl-substituted silyl group
- the R 6 -R 11 are independently represented as a C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted 5-containing one or more hetero atoms
- R 6 and R 7 are connected to adjacent groups to form a ring structure or not to form a ring;
- the substituents of the substitutable group are optionally selected from protium, deuterium, tritium, cyano, fluorine atoms, C 1 -C 20 alkyl groups, C 6 -C 20 aryl groups, those containing one or more heteroatoms One or more of 5 to 30 membered heteroaryl groups;
- the hetero atom is optionally selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
- R 1 to R 5 each independently represent the structures represented by the general formula (2) and the general formula (3);
- R 12 and R 13 are independently represented as methyl, ethyl, propyl, isopropyl, tert-butyl, butyl, pentyl, substituted or Unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted biphenyl, substituted or unsubstituted anthryl , Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrene, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted azabenzophenanthryl, substituted or unsubstituted azacarbazolyl, Substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted fluoride, benzyl,
- X 6 and X 9 are independently represented as oxygen atom, sulfur atom, -N(R 14 )-, -C(R 15 )(R 16 )- or -Si(R 17 )(R 18 )-;
- X 7 and X 8 can be independently represented as single bond, oxygen atom, sulfur atom, -N(R 14 )-, -C(R 15 )(R 16 )- or -Si(R 17 )(R 18 )-;
- Each occurrence of Z is the same or differently represented as N atom or CR 19 ;
- the R 14 -R 18 are independently represented as a C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted 5-containing one or more hetero atoms One of the 30-membered heteroaryl groups;
- the R 19 is the same or different from the hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, substituted or unsubstituted One of C 6 -C 20 aryl groups, substituted or unsubstituted 5-30 membered heteroaryl groups containing one or more heteroatoms; wherein two or more R 9 groups are connected to each other and form Ring or not ring;
- the general formula (4) and the general formula (5) are fused and connected by two adjacent positions marked with * and two adjacent positions marked with * in general formula (2) or (3);
- Ar 1 and Ar 2 independently represent one of a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
- the substituents of the substitutable group are optionally selected from protium, deuterium, tritium, cyano, fluorine atoms, C 1 -C 20 alkyl groups, C 6 -C 20 aryl groups, those containing one or more heteroatoms One or more of 5 to 30 membered heteroaryl groups;
- the hetero atom is optionally selected from one or more of oxygen atom, sulfur atom or nitrogen atom.
- the R 6 -R 16 independently represent methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene Group, substituted or unsubstituted naphthyridyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted Dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted azacarbazolyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrene Group, substitute
- the Ar 1 and Ar 2 are independently represented as substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Substituted terphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted Spirofluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted azacarbazolyl;
- the R and R 19 are independently represented as hydrogen atom, protium atom, deuterium atom, tritium atom, fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, butyl group, pentyl group Group, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Terphenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl;
- the substituent of the substitutable group is optionally selected from deuterium, fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, t-butyl, butyl, pentyl, phenyl, biphenyl , Terphenyl, naphthyl, furyl, dibenzofuranyl, carbazolyl, fluorenyl, naphthyridyl or pyridyl.
- the a+b+c+d+e 2 or 1.
- the Y 1 to Y 21 are expressed as the number of nitrogen atoms being 0, 1, or 2.
- the specific structure of the compound is:
- the application of the boron-containing organic compound in the preparation of organic electroluminescent devices is preferably, the application of the boron-containing organic compound in the preparation of organic electroluminescent devices.
- the organic electroluminescent device comprises at least one functional layer containing the boron-containing organic compound according to claims.
- an organic electroluminescent device includes a light-emitting layer, and the boron-containing organic compound is used as a host material or a doping material for the light-emitting layer, and is used to manufacture an organic electroluminescent device.
- an illumination or display element includes the organic electroluminescent device.
- the compound of the present invention uses boron as the backbone and connects the long-chain branched structure of the nitrogen heterocyclic derivative. Due to the different electron-donating ability of the branched group, the HOMO energy level of the overall structure of the compound can be adjusted freely, and the HOMO energy level is shallow.
- the compound can be used as a hole transport/electron blocking material; the material with a deep HOMO energy level can be used as a host material for a partial hole type light emitting layer.
- the boron group is an amphoteric group
- the branched chain is a long-chain structure, which breaks the symmetry of the molecular structure and avoids the aggregation between molecules
- the branched chain group of the compound of the present invention also has strong rigidity, therefore, the molecules are not easy to aggregate It is crystalline, has good film formation, and has a high glass transition temperature and thermal stability. Therefore, when the compound of the present invention is applied to an OLED device, it can maintain the stability of the film layer after the film is formed and improve the service life of the OLED device.
- the compound of the present invention has a high triplet energy level, which can effectively block energy loss and facilitate energy transfer. Therefore, when the compound of the present invention is used as an organic electroluminescent functional layer material in an OLED device, the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the life of the device is very obvious, and the OLED emits light The device has good application effect and good industrialization prospect.
- FIG. 1 is a schematic structural view of the materials listed in the present invention applied to an OLED device
- FIG. 2 is a graph of efficiency measured at different temperatures for devices prepared by the present invention and comparative devices.
- 1 is a transparent substrate layer
- 2 is an ITO anode layer
- 3 is a hole injection layer
- 4 is a hole transport layer
- 5 is an electron blocking layer
- 6 is a light emitting layer
- 7 is a hole blocking/electron transport layer
- 8 It is an electron injection layer
- 9 is a cathode reflective electrode layer.
- Elemental analysis structure (molecular formula C 18 H 14 BBrClN): theoretical value C, 58.36; H, 3.81; B, 2.92; Br, 21.57; Cl, 9.57; N, 3.78; test value C, 58.35; H, 3.86; B, 2.91; Br, 21.55; Cl, 9.56; N, 3.79.
- Elemental analysis structure (molecular formula C 30 H 20 B 2 BrN): theoretical value C, 72.64; H, 4.06; B, 4.36; Br, 16.11; N, 2.82; test value C, 72.65; H, 4.08; B, 4.35; Br, 16.13; N, 2.81.
- ESI-MS m/z (M + ): The theoretical value is 495.10, and the actual value is 485.39.
- the intermediate G was prepared by the synthesis method of intermediate G-1, and the specific structure is shown in Table 3.
- Elemental analysis structure (molecular formula C 52 H 34 B 2 N 4 ): theoretical values: C, 84.80; H, 4.65; B, 2.94; N, 7.61; test values C, 84.84; H, 4.63; B, 2.93; N, 7.60.
- HPLC-MS The molecular weight of the material is 736.30, and the measured molecular weight is 736.58.
- the compound of the present invention is used in a light-emitting device, has a high glass transition temperature (Tg) and triplet energy level (T1), and has suitable HOMO and LUMO energy levels, and can be used as a host and guest material of a light-emitting layer.
- Tg glass transition temperature
- T1 triplet energy level
- T1 HOMO and LUMO energy levels
- ⁇ Est refers to the difference between the singlet energy level and the triplet energy level of the material. It first measures the fluorescence emission spectrum and phosphorescence emission spectrum of the compound, and is calculated from the fluorescence emission peak and the phosphorescence emission peak (test equipment) : Using FLS980 fluorescence spectrometer of Edinburgh Instruments, Optistat DN-V2 cryogenic component of Oxford Instruments)
- the compound of the present invention has a smaller singlet-triplet energy level difference, so that the efficiency and lifespan of the OLED device using the compound of the present invention as a light-emitting layer material are improved.
- an electroluminescent device As shown in FIG. 1, an electroluminescent device, the preparation steps include:
- the hole injection layer material HAT-CN is evaporated by vacuum evaporation with a thickness of 10 nm, and this layer is used as the hole injection layer 3;
- the hole transport material HT-1 is evaporated by vacuum evaporation with a thickness of 60 nm, and this layer is the hole transport layer 4;
- the electron blocking material EB-1 is evaporated by vacuum evaporation, the thickness is 20 nm, and this layer is the electron blocking layer 5;
- the light-emitting layer 6 is vapor-deposited on the electron blocking layer 5, the host material is the compound GH-1, GH-2 prepared in the embodiment of the present invention, the doping material is H2, and the compound GH-1, GH-2 and H2 The mass ratio is 45:45:10 and the thickness is 30nm;
- the electron transport materials ET-1 and Liq are vapor-deposited by vacuum evaporation.
- the mass ratio of the two is 1:1 and the thickness is 40 nm.
- This organic material serves as hole blocking/electron transport Layer 7 use;
- an electron injection layer LiF is vacuum-evaporated with a thickness of 1 nm, which is an electron injection layer 8;
- the cathode Al (100 nm) is vacuum-evaporated, which is the cathode reflective electrode layer 9;
- Device Examples 2-30 and Comparative Example 1-2 are completely the same as the device Example 1 in the manufacturing process, and use the same substrate material and electrode material, the electrode material film thickness also remains the same, the difference is that the light The materials used for the layers are different. See Table 5 for specific data.
- the OLED device prepared by the material of the present invention has relatively stable efficiency when operated at low temperature.
- the device examples 1, 5, 27 and the device comparative examples 1 and 2 were tested for efficiency in the range of -10 to 80°C. The results are shown in the table. 7 and Figure 2.
- device examples 1, 5, 27 are device structures in which the materials of the present invention are matched with known materials. Compared with device comparative example 1 and device comparative example 2, not only is the low temperature efficiency high, but also During the temperature increase, the efficiency increases steadily.
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Abstract
本发明公开了一种含硼化合物及其在有机电致发光器件上的应用,该化合物为含有硼原子结构,且具有很强的刚性,分子间具有不易结晶、不易聚集、具有良好成膜性的特点;本发明化合物具有TADF特点,由于基团给电子能力强弱不同,因此,材料的HOMO能级有所不同,可作为不同功能层材料使用;另外,本发明化合物具有高的荧光量子效率,可有效产生辐射跃迁。因此,本发明化合物作为有机电致发光功能层材料应用于OLED器件后,器件的电流效率,功率效率和外量子效率均得到很大改善;同时,对于器件寿命提升非常明显。
Description
本发明涉及半导体技术领域,尤其是涉及一种含硼的化合物及其在有机电致发光器件上的应用。
当前,OLED显示技术已经在智能手机,平板电脑等领域获得应用,进一步还将向电视等大尺寸应用领域扩展,但是,和实际的产品应用要求相比,OLED器件的发光效率,使用寿命等性能还需要进一步提升。对于OLED发光器件提高性能的研究包括:降低器件的驱动电压,提高器件的发光效率,提高器件的使用寿命等。为了实现OLED器件的性能的不断提升,不但需要从OLED器件结构和制作工艺的创新,更需要OLED光电功能材料不断研究和创新,创制出更高性能OLED的功能材料。应用于OLED器件的OLED光电功能材料从用途上可划分为两大类,即电荷注入传输材料和发光材料,进一步,还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料,还可以将发光材料分为主体发光材料和掺杂材料。为了制作高性能的OLED发光器件,要求各种有机功能材料具备良好的光电特性,譬如,作为电荷传输材料,要求具有良好的载流子迁移率,高玻璃化转化温度等,作为发光层的主体材料要求材料具有良好双极性,适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构,产业上应用的OLED器件结构,则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层,也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料,空穴传输材料,发光材料,电子传输材料等,材料类型和搭配形式具有丰富性和多样性的特点。另外,对于不同结构的OLED器件搭配而言,所使用的光电功能材料具有较强的选择性,相同的材料在不同结构器件中的性能表现,也可能完全迥异。因此,针对当前OLED器件的产业应用要求,以及OLED器件的不同功能膜层,器件的光电特性需求,必须选择更适合,具有高性能的OLED功能材料或材料组合,才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言,目前OLED材料的发展还远远不够,落后于面板制造企业的要求,作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题,本发明提供了一种含硼的化合物及其在有机电致发光器件上的应用。本发明化合物含有硼结构,具有较高的玻璃化温度和分子热稳定性,合适的HOMO和LUMO能级,应用于OLED器件制作后,可有效提高器件的发光效率和OLED器件的使用寿命。
本发明的技术方案如下:
一种含硼有机化合物,所述化合物的结构如通式(1)所示:
通式(1)中,W
1、W
2、W
3各自独立的表示氮原子或硼原子,且W
1、W
2、W
3中有且仅有一个表示为氮原子;
a、b、c、d、e分别独立的表示为0或1,且a+b+c+d+e≥1;
X
1、X
2、X
3、X
4、X
5独立的表示为单键、硫原子、氧原子、
N(R
6)、B(R
7)、C(R
8)(R
9)或Si(R
10)(R
11);其中R
8与R
9、R
10与R
11相互连接成环或不成环;X
1、X
2、X
3、X
4、X
5中至少有一个不表示为单键;
L相同或不同地表示表示为取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚萘啶基、取代或未取代的亚吡啶基、取代或未取代的亚二联苯基、取代或未取代的亚三联苯基、取代或未取代的亚咔唑基、取代或未取代的亚二苯并呋喃基、取代或未取代的亚螺芴基、取代或未取代的亚二甲基芴基、取代或未取代的亚二苯基芴基;
α、β、γ、η、θ各自独立的表示为1、2或3;
当a、b、c、d、e分别独立的表示为0时,Y
1至Y
21各自独立的表示为氮原子或C-R或C-L-R
1或C-L-R
2或C-L-R
3或C-L-R
4或C-L-R
5;当a、b、c、d、e分别独立的表示为1时,Y
21、Y
1,Y
16、Y
17、Y
13、Y
14、Y
8、Y
9、Y
4、Y
5只表示为碳原子,其余可各自独立的表示为氮原子或C-R或C-L-R
1或C-L-R
2或C-L-R
3或C-L-R
4或C-L-R
5;
所述R表示为氢原子、氕、氘、氚、氰基、卤素原子、C
1-C
20烷基、C
1-C
20烷基取代的硅烷基、取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的杂芳基、C
6-C
20的芳基或5至30元杂芳基取代的胺基中的一种;
R
1至R
5分别独立地代表氢原子、氕原子、氘原子、氚原子、氟原子、氰基、C
1-C
20烷基、C
1-C
20烷基取代的硅烷基、取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的杂芳基、C
6-C
20的芳基或5至30元杂芳基取代的胺基中的一种;
所述R
6-R
11分别独立的表示为C
1-C
20的烷基、取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;R
6、R
7与相邻基团连接形成环结构或者不成环;
所述可取代基团的取代基任选自氕、氘、氚、氰基、氟原子、C
1-C
20的烷基、C
6-C
20的芳基、含有一个或多个杂原子的5至30元杂芳基中的一种或多种;
所述杂原子任选自氧原子、硫原子或氮原子中的一中或多种。
作为本发明进一步改进,R
1至R
5各自独立地表示通式(2)和通式(3)所示结构;
通式(2)和通式(3)中,所述R
12、R
13分别独立地表示为甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的咔唑基、取代或未取代的二苯并呋喃基、取代或未取代的联苯基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的苯并菲基、取代或未取代的氮杂苯并菲基、取代或未取代的氮杂咔唑基、取代或未取代苯并咔唑基、取代或未取代的芴基、取代或未取代的吡啶基、取代或未取代的萘啶基、通式(4)、通式(5)或通式(6)所示基团;R
12、R
13相同或不同;s、t表示0或1;
X
6、X
9分别独立的表示为氧原子、硫原子、-N(R
14)-、-C(R
15)(R
16)-或-Si(R
17)(R
18)-;
X
7、X
8分别独立的还可以表示为单键、氧原子、硫原子、-N(R
14)-、-C(R
15)(R
16)-或-Si(R
17)(R
18)-;
Z每次出现相同或不同地表示为N原子或C-R
19;
所述R
14-R
18分别独立的表示为C
1-C
20的烷基、取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;
所述R
19相同或不同地选自氢原子、氕原子、氘原子、氚原子、氟原子、氰基、C
1-C
20的烷基、C
2-C
20的烯烃基、取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;其中两个或更多个R
9基团彼此连接并且形成环或者不成环;
通式(4)和通式(5)通过*标记的两个相邻位置与通式(2)或通式(3)中*标记的两个相邻的位置稠合连接;
Ar
1、Ar
2分别独立地代表取代或未取代的C
6-C
20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;
所述可取代基团的取代基任选自氕、氘、氚、氰基、氟原子、C
1-C
20的烷基、C
6-C
20的芳基、含有一个或多个杂原子的5至30元杂芳基中的一种或多种;
所述杂原子任选自氧原子、硫原子或氮原子中的一中或多种。
进一步优选,所述R
6-R
16分别独立的表示为甲基、乙基、丙基、丁基、叔丁基、戊基、己基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、取代或未取代的吡啶基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的芴基、取代或未取代的二苯并呋喃基、取代或未取代的咔唑基、取代或未取代的螺芴基、取代或未取代的氮杂咔唑基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的苯并菲基、取代或未取代的氮杂苯并菲基、取代或未取代的氮杂二苯并呋喃基、取代或未取代苯并咔唑基;
所述Ar
1、Ar
2分别独立的表示为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的吡啶基、取代或未取代的咔唑基、取代或未取代的二甲基芴基、取代或未取代的二苯基芴基、取代或未取代的螺芴基、取代或未取代的二苯并呋喃基、取代或未取代的二苯并噻吩基、取代或未取代的氮杂咔唑基;
所述R、R
19分别独立的表示为氢原子、氕原子、氘原子、氚原子、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、取代或未取代的吡啶基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的咔唑基、取代或未取代的二苯并呋喃基;
所述可取代基团的取代基任选自氘、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、苯基、二联苯基、三联苯基、萘基、呋喃基、二苯并呋喃基、咔唑基、芴基、萘啶基或吡啶基中的一种或多种。
进一步优选,所述a+b+c+d+e=2或1。
进一步优选,所述Y
1至Y
21表示为氮原子的个数为0、1或2。
进一步优选,所述化合物具体结构为:
进一步优选,一所述的含硼有机化合物在制备有机电致发光器件中的应用。
进一步优选,所述有机电致发光器件包括至少一层功能层含有权利要求所述的含硼有机化合物。
进一步优选,一种有机电致发光器件,包含发光层,所述含硼有机化合物作为发光层的主体材料或掺杂材料,用于制作有机电致发光器件。
进一步优选,一种照明或显示元件,包括所述的有机电致发光器件。
本发明有益的技术效果在于:
1.本发明化合物以硼为骨架,连接氮杂环衍生物长支链结构,由于支链基团给电子能力强弱不同,使化合物整体结构的HOMO能级可自由调整,HOMO能级浅的化合物可作为空穴传输/电子阻挡材料使用;HOMO能级深的材料可作为偏空穴型发光层主体材料使用。
另外,硼基团为双性基团,支链为长链结构,破坏分子结构对称性,避免分子间的聚集作用;本发明化合物的支链基团也具有很强刚性,因此,分子不易聚集结晶、具有良好的成膜性,并具有高的玻璃化温度及热稳定性,所以,本发明化合物应用于OLED器件时,可保持材料成膜后的膜层稳定性,提高OLED器件使用寿命。
2.本发明化合物具有高的三线态能级,可有效阻挡能量损失、并利于能量传递。因此,本发明所述化合物作为有机电致发光功能层材料应用于OLED器件后,器件的电流效率,功率效率和外量子效率均得到很大改善;同时,对于器件寿命提升非常明显,在OLED发光器件中具有良好的应用效果,具有良好的产业化前景。
图1为本发明所列举的材料应用于OLED器件的结构示意图;
图2为本发明制备的器件和对比器件在不同温度下测量的效率曲线图。
其中,1为透明基板层,2为ITO阳极层,3为空穴注入层,4为空穴传输层,5为电子阻挡层,6为发光层,7为空穴阻挡/电子传输层,8为电子注入层,9为阴极反射电极层。
实施例1:中间体G的合成:以中间体G1的合成为例:
(1)250mL的三口瓶,在通入氮气的气氛下,加入0.01mol原料A-1,0.015mol原料B-1,用混合溶剂溶解(90ml甲苯,45ml乙醇),然后加入0.03mol Na
2CO
3水溶液(2M),通氮气搅拌1小时,然后加入0.0001mol Pd(PPh
3)
4,加热回流15小时,取样点板,反应完全。自然冷却,过滤,滤液旋蒸,过硅胶柱,得到中间体J-1,纯度96.4%,收率83.7%。元素分析结构(分子式C
18H
14BBrClN):理论值C,58.36;H,3.81;B,2.92;Br,21.57;Cl,9.57;N,3.78;测试值C,58.35;H,3.86;B,2.91;Br,21.55;Cl,9.56;N,3.79。ESI-MS(m/z)(M+):理论值为369.01,实测值为369.59。
(2)取0.1mol中间体J-1和0.12mol苯,加入0.12mol叔丁基锂,120ml叔丁基苯,60℃保温2小时后,降温到室温条件下,滴加0.12mol BBr
3充分反应半个小时,加入水,析出固体,依次使用正已烷洗涤,乙醇进行重结晶,得到化合物G-2。HPLC纯度96.3%,收率79.7%。元素分析结构(分子式C
30H
20B
2BrN):理论值C,72.64;H,4.06;B,4.36;Br,16.11;N,2.82;测试值C,72.65;H,4.08;B,4.35;Br,16.13;N,2.81。ESI-MS(m/z)(M
+):理论值为495.10,实测值为485.39。
以中间体G-1的合成方法制备中间体G,具体结构如表3所示。
表3
实施例2:化合物H2的合成:
在250ml的三口瓶中,通氮气保护下,加入0.01mol中间体G-1,0.012mol原料C1,150ml甲苯搅拌混合,然后加入5×10
-5molPd
2(dba)
3,5×10
-5mol P(t-Bu)
3,0.03mol叔丁醇钠,加热至105℃,回流反应24小时,取样点板,显示无溴代物剩余,反应完全;自然冷却至室温,过滤,滤液旋蒸至无馏分,过中性硅胶柱,得到目标产物,HPLC纯度99.76%,收率76.1%。元素分析结构(分子式C
52H
34B
2N
4):理论值:C,84.80;H,4.65;B,2.94;N,7.61;测试值C,84.84;H,4.63;B,2.93;N,7.60。HPLC-MS:材料分子量为736.30,实测分子量736.58。
实施例3:化合物H43的合成:
将0.01mol中间体G-2和0.012mol原料C2溶解于甲苯和乙醇的150mL(V甲苯:V乙醇=5:1)混合溶液中,除氧后加入0.0002mol Pd(PPh
3)
4和0.02mol Na
2CO
3,在通入氮气的气氛下110℃反应24个小时,取样点板,待原料反应完全后,冷却、过滤,将滤液旋蒸除去溶剂,粗产品过硅胶柱,得到化合物H43;元素分析结构(分子式C
51H
37B
2N):理论值:C,89.36;H,5.44;B,3.15;N,2.04;测试值C,89.28;H,3.18;B,3.15;N,2.07。HPLC-MS:材料分子量为685.31,实测分子量685.47。
实施例4:化合物H84的合成:同上
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-3代替中间体G-2,用原料C3替换原料C2;元素分析结构(分子式C
54H
29B
2NO
4):理论值:C,83.43;H,3.76;B,2.78;N,1.80;测试值C,83.44;H,3.78;B,2.75;N,1.82。HPLC-MS:材料分子量为777.23,实测分子量777.60。
实施例5:化合物H120的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-4代替中间体G-2,用原料C4替换原料C2;元素分析结构(分子式C
48H
25B
2NO
4):理论值:C,83.43;H,3.76;B,2.78;N,1.80;测试值C,83.41;H,3.75;B,2.79;N,1.82。HPLC-MS:材料分子量为701.20,实测分子量701.35。
实施例6:化合物H204的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-5代替中间体G-2,用原料C5替换原料C2;元素分析结构(分子式C
66H
45B
2N
3):理论值:C,87.91;H,5.03;B,2.40;N,4.66;测试值C,87.93;H,5.06;B,2.41;N,4.65。HPLC-MS:材料分子量为901.38,实测分子量901.77。
实施例7:化合物H257的合成:
按实施例2中化合物H2的合成方法制备,不同点在于用中间体G-6代替中间体G-1,用原料C6替换原料C1;元素分析结构(分子式C
65H
42B
2N
4):理论值:C,86.68;H,4.70;B,2.40;N,6.22;测试值C,86.72;H,4.66;B,2.41;N,6.21。HPLC-MS:材料分子量为900.36,实测分子量900.61。
实施例8:化合物H260的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-6代替中间体G-2,用原料C7替换原料C2;元素分析结构(分子式C
60H
33B
2N
3O
2):理论值:C,84.83;H,3.92;B,2.54;N,4.95;测试值C,84.84;H,3.91;B,2.52;N,4.96。HPLC-MS:材料分子量为849.28,实测分子量849.58。
实施例9:化合物H252的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-6代替中间体G-2,用原料C8替换原料C2;元素分析结构(分子式C
66H
38B
2N
4O):理论值:C,85.73;H,4.14;B,2.34;N,6.06;测试值C,85.77;H,4.12;B,2.33;N,6.01。HPLC-MS:材料分子量为924.68,实测分子量925.27。
实施例10:化合物H254的合成:
按实施例2中化合物H2的合成方法制备,不同点在于用中间体G-6代替中间体G-1,用原料C9替换原料C1;元素分析结构(分子式C
57H
38B
2N
4):理论值:C,85.52;H,4.78;B,2.70;N,7.00;测试值C,85.54;H,4.79;B,2.67;N,7.01。HPLC-MS:材料分子量为800.58,实测分子量800.73。
实施例11:化合物H270的合成:
按实施例2中化合物H2的合成方法制备,不同点在于用中间体G-7代替中间体G-1,用原料C10替换原料C1;元素分析结构(分子式C
52H
33B
2N
3):理论值:C,86.57;H,4.61;B,3.00;N,5.82;测试值C,86.59;H,4.60;B,3.02;N,5.80。HPLC-MS:材料分子量为721.29,实测分子量721.56。
实施例12:化合物H316的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-8代替中间体G-2,用原料C11替换原料C2;元素分析结构(分子式C
48H
30B
2N
2S):理论值:C,83.74;H,4.39;B,3.14;N,4.07;S,4.66;测试值C,83.75;H,4.40;B,3.12;N,4.48。HPLC-MS:材料分子量为688.23,实测分子量688.46。
实施例13:化合物H344的合成:
按实施例2中化合物H2的合成方法制备,不同点在于用中间体G-9代替中间体G-1,用原料C12替换原料C1;元素分析结构(分子式C
56H
35B
2N
3):理论值:C,87.18;H,4.57;B,2.80;N,5.45;测试值C,87.16;H,4.58;B,2.82;N,5.43。HPLC-MS:材料分子量为771.30,实测分子量771.66。
实施例14:化合物H351的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-10代替中间体G-2,用原料C13替换原料C2;元素分析结构(分子式C
48H
30B
2N
2O):理论值:C,85.74;H,4.50;B,3.22;N,4.17;测试值C,85.76;H,4.51;B,3.23;N,4.16。HPLC-MS:材料分子量为672.25,实测分子量672.62。
实施例15:化合物H358的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-11代替中间体G-2,用原料C14替换原料C2;元素分析结构(分子式C
54H
28B
2N
2O
4):理论值:C,82.05;H,3.57;B,2.74;N,3.54;测试值C,82.08;H,3.55;B,2.73;N,3.56。HPLC-MS:材料分子量为790.22,实测分子量790.69。
实施例16:化合物H362的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-12代替中间体G-2,用原料C15替换原料C2;元素分析结构(分子式C
60H
40B
2N
2O
2):理论值:C,85.53;H,4.79;B,2.57;N,3.32;测试值C,85.54;H,4.81;B,2.54;N,3.33。HPLC-MS:材料分子量为842.61,实测分子量842.98。
实施例17:化合物H363的合成:
按实施例3中化合物H2的合成方法制备,不同点在于用中间体G-12代替中间体G-2,用原料C16替换 原料C2;元素分析结构(分子式C
55H
34B
2N
2O
3):理论值:C,83.36;H,4.32;B,2.73;N,3.53;测试值C,83.35;H,4.35;B,2.71;N,3.52。HPLC-MS:材料分子量为792.51,实测分子量792.94。
实施例18:化合物H364的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-13代替中间体G-2,用原料C17替换原料C2;元素分析结构(分子式C
71H
45B
2N
3):理论值:C,88.67;H,4.72;B,2.25;N,4.37;测试值C,88.69;H,4.68;B,2.26;N,4.38。HPLC-MS:材料分子量为961.38,实测分子量961.61。
实施例19:化合物H367的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-14代替中间体G-2,用原料C18替换原料C2;元素分析结构(分子式C
64H
41B
2N):理论值:C,90.90;H,4.89;B,2.56;N,1.66;测试值C,90.92;H,4.88;B,2.56;N,1.65。HPLC-MS:材料分子量为845.34,实测分子量845.70。
实施例20:化合物H368的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-15代替中间体G-2,用原料C19替换原料C2;元素分析结构(分子式C
55H
31B
2N):理论值:C,90.81;H,4.30;B,2.97;N,1.93;测试值C,90.82;H,4.31;B,2.98;N,1.90。HPLC-MS:材料分子量为727.26,实测分子量727.47。
实施例21:化合物H371的合成:
按实施例3中化合物H43的合成方法制备,不同点在于用中间体G-16代替中间体G-2,用原料C19替换原料C2;元素分析结构(分子式C
55H
31B
2N):理论值:C,90.81;H,4.30;B,2.97;N,1.93;测试值C,90.80;H,4.30;B,2.99;N,1.92。HPLC-MS:材料分子量为727.26,实测分子量727.58。
本发明化合物在发光器件中使用,具有高的玻璃化转变温度(Tg)和三线态能级(T1),合适的HOMO、LUMO能级,可作为发光层主体和客体材料使用。对本发明上述实施例制备的化合物分别进行热性能、T1能 级以及HOMO能级测试,结果如表4所示。
表4
化合物 | △Est | 化合物 | △Est | 化合物 | △Est | 化合物 | △Est |
化合物H2 | 0.13 | 化合物H257 | 0.08 | 化合物H316 | 0.12 | 化合物H363 | 0.12 |
化合物H43 | 0.11 | 化合物H260 | 0.13 | 化合物H344 | 0.11 | 化合物H364 | 0.14 |
化合物H84 | 0.09 | 化合物H252 | 0.09 | 化合物H351 | 0.13 | 化合物H367 | 0.08 |
化合物H120 | 0.11 | 化合物H256 | 0.12 | 化合物H358 | 0.12 | 化合物H368 | 0.11 |
化合物H204 | 0.09 | 化合物H270 | 0.11 | 化合物H362 | 0.10 | 化合物H371 | 0.12 |
注:△Est:是指材料的单线态能级与三线态能级的差值,它先分别测试化合物的荧光发射光谱和磷光发射光谱,并由荧光发射峰和磷光发射峰计算得到(测试设备:利用Edinburgh Instruments的FLS980荧光光谱仪,Oxford Instruments的Optistat DN-V2低温组件)
由表4数据可知,本发明的化合物具有较小的单线态-三线态能级差,使得应用本发明化合物作为发光层材料的OLED器件效率和寿命得到提升。
器件的制备:
以下通过器件实施例1-30和器件比较例1-2详细说明本发明合成的化合物在器件中作为发光层材料的应用效果。器件实施例2-30以及器件比较例1-2与器件实施例1相比,所述器件的制作工艺完全相同,并且所采用了相同的基板材料和电极材料,电极材料的膜厚也保持一致,所不同的是器件中发光层材料发生了改变。器件叠层结构如表5所示,各器件的性能测试结果见表6和表7。
器件实施例1
如图1所示,一种电致发光器件,其制备步骤包括:
a)清洗透明基板层1上的ITO阳极层2,分别用去离子水、丙酮、乙醇超声清洗各15分钟,然后在等离子体清洗器中处理2分钟;
b)在ITO阳极层2上,通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN,厚度为10nm,这层作为空穴注入层3;
c)在空穴注入层3上,通过真空蒸镀方式蒸镀空穴传输材料HT-1,厚度为60nm,该层为空穴传输层4;
d)在空穴传输层4上,通过真空蒸镀方式蒸镀电子阻挡材料EB-1,厚度为20nm,该层为电子阻挡层5;
e)在电子阻挡层5之上蒸镀发光层6,主体材料为本发明实施例制备的化合物GH-1、GH-2,掺杂材料为H2,化合物GH-1、GH-2和H2的质量比为45:45:10,厚度为30nm;
f)在发光层6之上,通过真空蒸镀方式蒸镀电子传输材料ET-1、Liq,两者的质量比为1:1,厚度为40nm,这层有机材料作为空穴阻挡/电子传输层7使用;
g)在空穴阻挡/电子传输层7之上,真空蒸镀电子注入层LiF,厚度为1nm,该层为电子注入层8;
h)在电子注入层8之上,真空蒸镀阴极Al(100nm),该层为阴极反射电极层9;
按照上述步骤完成电致发光器件的制作后,测量器件性能其结果见表4所示。相关材料的分子结构式如下所示:
器件实施例2-30和比较例1-2与器件实施例1的器件的制作工艺完全相同,并且采用了相同的基板材料和电极材料,电极材料的膜厚也保持一致,不同之处在于发光层所用的材料不相同。具体的数据参见表5。
表5
各器件实施例和比较例器件的效率和寿命数据见表6所示。
表6
由表6的结果可以看出,本发明制备的有机化合物可应用于OLED发光器件制作,并且与器件比较例1、器件比较例2相比,无论是效率还是寿命均比已知OLED材料获得较大改观,特别是器件的使用寿命获得较大的提升。
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定,将器件实施例1、5、27和器件比较例1、2在-10~80℃区间进行效率测试,所得结果如表7和图2所示。
表7
从表7和图2的数据可知,器件实施例1、5、27为本发明材料和已知材料搭配的器件结构,和器件比较例1、器件比较例2相比,不仅低温效率高,而且在温度升高过程中,效率平稳升高。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
- 一种含硼有机化合物,其特征在于,所述化合物的结构如通式(1)所示:通式(1)中,W 1、W 2、W 3各自独立的表示氮原子或硼原子,且W 1、W 2、W 3中有且仅有一个表示为氮原子;a、b、c、d、e分别独立的表示为0或1,且a+b+c+d+e≥1;X 1、X 2、X 3、X 4、X 5独立的表示为单键、硫原子、氧原子、 N(R 6)、B(R 7)、C(R 8)(R 9)或Si(R 10)(R 11);其中R 8与R 9、R 10与R 11相互连接成环或不成环;X 1、X 2、X 3、X 4、X 5中至少有一个不表示为单键;L相同或不同地表示表示为取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的亚萘啶基、取代或未取代的亚吡啶基、取代或未取代的亚二联苯基、取代或未取代的亚三联苯基、取代或未取代的亚咔唑基、取代或未取代的亚二苯并呋喃基、取代或未取代的亚螺芴基、取代或未取代的亚二甲基芴基、取代或未取代的亚二苯基芴基;α、β、γ、η、θ各自独立的表示为1、2或3;当a、b、c、d、e分别独立的表示为0时,Y 1至Y 21各自独立的表示为氮原子或C-R或C-L-R 1或C-L-R 2或C-L-R 3或C-L-R 4或C-L-R 5;当a、b、c、d、e分别独立的表示为1时,Y 21、Y 1,Y 16、Y 17、Y 13、Y 14、Y 8、Y 9、Y 4、Y 5只表示为碳原子,其余可各自独立的表示为氮原子或C-R或C-L-R 1或C-L-R 2或C-L-R 3或C-L-R 4或C-L-R 5;所述R表示为氢原子、氕、氘、氚、氰基、卤素原子、C 1-C 20烷基、C 1-C 20烷基取代的硅烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的杂芳基、C 6-C 20的芳基或5至30元杂芳基取代的胺基中的一种;R 1至R 5分别独立地代表氢原子、氕原子、氘原子、氚原子、氟原子、氰基、C 1-C 20烷基、C 1-C 20烷基取代的硅烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的杂芳基、C 6-C 20的芳基或5至30元杂芳基取代的胺基中的一种;所述R 6-R 11分别独立的表示为C 1-C 20的烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;R 6、R 7与相邻基团连接形成环结构或者不成环;所述可取代基团的取代基任选自氕、氘、氚、氰基、氟原子、C 1-C 20的烷基、C 6-C 20的芳基、含有一个或多个杂原子的5至30元杂芳基中的一种或多种;所述杂原子任选自氧原子、硫原子或氮原子中的一中或多种。
- 根据权利要求1所述的一种含硼有机化合物,其特征在于,R 1至R 5各自独立地表示通式(2)和通式(3)所示结构;通式(2)和通式(3)中,所述R 12、R 13分别独立地表示为甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的咔唑基、取代或未取代的二苯并呋喃基、取代或未取代的联苯基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的苯并菲基、取代或未取代的氮杂苯并菲基、取代或未取代的氮杂咔唑基、取代或未取代苯并咔唑基、取代或未取代的芴基、取代或未取代的吡啶基、取代或未取代的萘啶基、通式(4)、通式(5)或通式(6)所示基团;R 12、R 13相同或不同;s、t表示0或1;X 6、X 9分别独立的表示为氧原子、硫原子、-N(R 14)-、-C(R 15)(R 16)-或-Si(R 17)(R 18)-;X 7、X 8分别独立的还可以表示为单键、氧原子、硫原子、-N(R 14)-、-C(R 15)(R 16)-或-Si(R 17)(R 18)-;Z每次出现相同或不同地表示为N原子或C-R 19;所述R 14-R 18分别独立的表示为C 1-C 20的烷基、取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;所述R 19相同或不同地选自氢原子、氕原子、氘原子、氚原子、氟原子、氰基、C 1-C 20的烷基、C 2-C 20的烯烃基、取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;其中两个或更多个R 9基团彼此连接并且形成环或者不成环;通式(4)和通式(5)通过*标记的两个相邻位置与通式(2)或通式(3)中*标记的两个相邻的位置稠合连接;Ar 1、Ar 2分别独立地代表取代或未取代的C 6-C 20的芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种;所述可取代基团的取代基任选自氕、氘、氚、氰基、氟原子、C 1-C 20的烷基、C 6-C 20的芳基、含有一个或多个杂原子的5至30元杂芳基中的一种或多种;所述杂原子任选自氧原子、硫原子或氮原子中的一中或多种。
- 根据权利要求1所述的一种含硼化合物,其特征在于,所述R 6-R 16分别独立的表示为甲基、乙基、丙基、丁基、叔丁基、戊基、己基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、取代或未取代的吡啶基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的芴基、取代或未取代的二苯并呋喃基、取代或未取代的咔唑基、取代或未取代的螺芴基、取代或未取代的氮杂咔唑基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的苯并菲基、取代或未取代的氮杂苯并菲基、取代或未取代的氮杂二苯并呋喃基、取代或未取代苯并咔唑基;所述Ar 1、Ar 2分别独立的表示为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、 取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的吡啶基、取代或未取代的咔唑基、取代或未取代的二甲基芴基、取代或未取代的二苯基芴基、取代或未取代的螺芴基、取代或未取代的二苯并呋喃基、取代或未取代的二苯并噻吩基、取代或未取代的氮杂咔唑基;所述R、R 19分别独立的表示为氢原子、氕原子、氘原子、氚原子、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的萘啶基、取代或未取代的吡啶基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的咔唑基、取代或未取代的二苯并呋喃基;所述可取代基团的取代基任选自氘、氟原子、氰基、甲基、乙基、丙基、异丙基、叔丁基、丁基、戊基、苯基、二联苯基、三联苯基、萘基、呋喃基、二苯并呋喃基、咔唑基、芴基、萘啶基或吡啶基中的一种或多种。
- 根据权利要求1所述的含硼化合物,其特征在于,所述a+b+c+d+e=2或1。
- 根据权利要求1所述的含硼化合物,其特征在于,所述Y 1至Y 21表示为氮原子的个数为0、1或2。
- 一种如权利要求1-6任一项所述的含硼有机化合物在制备有机电致发光器件中的应用。
- 一种有机电致发光器件,其特征在于,所述有机电致发光器件包括至少一层功能层含有权利要求1-6任一项所述的含硼有机化合物。
- 根据权利要求7所述的有机电致发光器件,包含发光层,其特征在于,所述权利要求1-6所述的含硼有机化合物作为发光层的主体材料或掺杂材料,用于制作有机电致发光器件。
- 一种照明或显示元件,其特征在于,包括如权利要求7-9所述的有机电致发光器件。
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