CN113234098A - Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof - Google Patents
Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof Download PDFInfo
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- CN113234098A CN113234098A CN202110545959.3A CN202110545959A CN113234098A CN 113234098 A CN113234098 A CN 113234098A CN 202110545959 A CN202110545959 A CN 202110545959A CN 113234098 A CN113234098 A CN 113234098A
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- emitting
- boron
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- 239000000463 material Substances 0.000 title claims abstract description 92
- 230000003111 delayed effect Effects 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- 125000003118 aryl group Chemical group 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 31
- 125000001424 substituent group Chemical group 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 125000004986 diarylamino group Chemical group 0.000 claims description 6
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 3
- 239000010409 thin film Substances 0.000 claims 2
- 239000002346 layers by function Substances 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- -1 half-yl Chemical group 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- 125000000392 cycloalkenyl group Chemical group 0.000 description 20
- 125000001072 heteroaryl group Chemical group 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 125000003342 alkenyl group Chemical group 0.000 description 15
- 125000000304 alkynyl group Chemical group 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 125000003396 thiol group Chemical class [H]S* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 125000000464 thioxo group Chemical group S=* 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OFXSXYCSPVKZPF-UHFFFAOYSA-N methoxyperoxymethane Chemical compound COOOC OFXSXYCSPVKZPF-UHFFFAOYSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 3
- 235000012736 patent blue V Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 1
- 125000004502 1,2,3-oxadiazolyl group Chemical group 0.000 description 1
- 125000004511 1,2,3-thiadiazolyl group Chemical group 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- 125000004506 1,2,5-oxadiazolyl group Chemical group 0.000 description 1
- 125000004517 1,2,5-thiadiazolyl group Chemical group 0.000 description 1
- 125000001781 1,3,4-oxadiazolyl group Chemical group 0.000 description 1
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- PCMMSLVJMKQWMQ-UHFFFAOYSA-N 2,4-dibromopyridine Chemical compound BrC1=CC=NC(Br)=C1 PCMMSLVJMKQWMQ-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910004749 OS(O)2 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- YVGPBJXKKGORJD-UHFFFAOYSA-N [B].[N].[O] Chemical compound [B].[N].[O] YVGPBJXKKGORJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical group F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
The invention discloses an organic luminescence or thermal induced delayed fluorescence material containing a nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof. The organic luminescent material takes a high electrophilic nitrogen difluoride-boron-oxygen heterocyclic structure unit as an acceptor, is combined with different donors, can form a thermally induced delayed fluorescent material with easily adjustable luminescent color and high quantum efficiency, and has huge application prospect in the field of OLED materials.
Description
Technical Field
The invention belongs to the field of organic luminescent materials, and particularly relates to an organic luminescent or thermal induced delayed fluorescent material containing a nitrogen difluoride-boron-oxapolycyclic acceptor structural unit, which can be used in the fields of OLED display and illumination.
Background
Organic Light-Emitting diodes (OLEDs) are also called Organic Light-Emitting devices (Organic Light-Emitting devices) or Organic Electroluminescent devices (Organic Electroluminescent devices). The organic electroluminescence is a luminescence phenomenon that under the action of a forward bias electric field, an organic small molecule, a metal organic complex molecule or a polymer molecule luminescent material directly converts electric energy into light energy. The OLED is self-luminous, does not need a backlight source and saves energy; the LED display also has the characteristics of high response speed, low driving voltage, high luminous efficiency and resolution, wide visual angle, high contrast and the like; in addition, the substrate can be made of cheap glass, metal or even flexible plastic, so that the substrate has the advantages of low cost, simple production process, large-area production and the like, becomes a new generation of full-color display and illumination technology, has wide and huge application prospect in the fields of mobile phones, computers, televisions, digital cameras, GPS, bendable and foldable electronic products and illumination, and is widely valued by the academic and industrial fields.
The luminescent material adopted by the early device is mainly a first-generation organic micromolecule fluorescent material, and spin statistics quantum theory shows that the internal quantum efficiency of the electroluminescent theory of the fluorescent material is only 25%, so that the application of the fluorescent material in the OLED is limited. Professor Forrest and professor Thompson in the united states of 1998 realized the phenomenon of phosphorescent electroluminescence of metal platinum organic complex molecules at room temperature (Nature,1998,395,151); in the same year, the horse in China professor photofabrication and the professor shigaku report that phosphorescence electroluminescence of metal osmium complexes (Synth. Met.,1998,94,245), which are the second generation phosphorescent materials, is also reported. The material utilizes the strong spin-orbit coupling of heavy metal atoms to effectively promote the intersystem crossing of electrons from singlet state to triplet state, so that the OLED device can fully utilize all singlet state and triplet state excitons (exiton) generated by electric excitation, and the theoretical internal quantum efficiency of the luminescent material can reach 100%. Professor Adachi in japan in 2009 developed a novel third generation luminescent material, namely a Thermally Activated Delayed Fluorescence (TADF) material, and by reasonable structural design, a light emitting material having a very small singlet-triplet energy system (Δ E) was obtainedST) Organic molecules, heat in the surrounding environmentWith the excitation of the amount, the exciton can be transited from the triplet state to the singlet state, so that all excitons can be fully utilized, and theoretically, the internal quantum efficiency can also reach 100% (adv. mater, 2009,21,4802), and the device efficiency of doping such materials also reaches the performance of the phosphorescent device (nat. photonics,2014,8, 326). Since then, such materials have gained a great deal of attention.
Although the metal organic phosphorescent materials have been developed greatly, and the iridium complex phosphorescent materials for red and green lights have been applied to commercial electronic products, the metal phosphorescent materials which can meet the commercial requirements in terms of quantum efficiency and stability are extremely limited, and especially the blue light phosphorescent materials have difficulty reaching the requirements of commercial application; in addition, rare heavy metal materials are extremely expensive and have limited resources, which is a serious disadvantage. Therefore, the development of new pure organic luminescent materials, especially high-efficiency thermal delayed fluorescent materials, is urgently needed to solve the above problems; meanwhile, the design and development of novel efficient blue-light thermally-induced delayed fluorescent materials are also important problems in the field of OLEDs.
Disclosure of Invention
The invention aims to provide a donor-acceptor-based nitrogen-boron-oxygen-containing polycyclic aromatic hydrocarbon compound luminescent material or a thermally-induced delayed fluorescent material, which can be used in the fields of OLED display and illumination.
The invention provides an organic luminescent or thermal induced delayed fluorescent material containing a nitrogen difluoride-boron-oxapolycyclic acceptor structural unit as shown in a formula (1):
wherein,
the nitrogen, the boron and the oxygen are sequentially connected to form a bond, and the boron is connected with the two fluorine atoms to form a bond to form a stable boron difluoride structure;
Raand RbEach independently represents hydrogen, deuterium, alkyl of C1-C24, alkoxy of C1-C24, cycloalkyl of C1-C24, ether of C1-C24, heterocyclic of C1-C24, aryl of C1-C24, aryloxy of C1-C24A group, a halogen, a mono or dialkylamino group, a mono or diarylamino group, a cyano group, or a combination thereof;
m and n are respectively substituent RaAnd RbM is an integer of 0 to 4, n is an integer of 0 to 3;
the donor D may be one of the following structures:
wherein,
R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14and R15Each independently hydrogen, deuterium, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 cycloalkyl, C1-C24 ether, C1-C24 heterocyclic group, C1-C24 aryl, C1-C24 aryloxy, halogen, silicon group, mono-or dialkylamino group, mono-or diarylamino group, cyano group or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
o, p, q, R, s, t, u, v, w, x, y and z are substituents R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14、R15O and p are each independently an integer of 0 to 5; q, r, s, t, u, v, w, x, y and z are each independently integers of 0 to 4.
Further, preferably, the substituent R is1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14And R15Each independently hydrogen, deuterium, alkyl of C1-C24, alkoxy of C1-C24, cycloalkyl of C1-C24, heterocyclic of C1-C24, aryl of C1-C24, aryloxy of C1-C24, mono-or dialkylamino, mono-or diarylamino, cyano.
Still further, in some embodiments of the present invention, an organic light-emitting or thermally-induced delayed fluorescence material containing a type of nitrogen difluoride-boron-oxapolycyclic acceptor structural unit has a structure selected from one of:
the organic luminescent or thermal induced delayed fluorescence material containing the nitrogen difluoride-boron-oxapolycyclic acceptor structural unit is neutral in electricity.
The linking atom used in the present invention can link two groups, for example, N and C groups. The linking atom can optionally (if valency permits) have other chemical moieties attached. For example, in one aspect, oxygen does not have any other chemical group attached because once bonded to two atoms (e.g., N or C) valences have been satisfied. Conversely, when carbon is a linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ═ O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.
The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more, identical or different for suitable organic compounds. For the purposes of the present invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the atom being substituted and the allowed valence of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless explicitly stated to the contrary.
In defining the terms, "R1”、“R2”、“R3"and" R4"used as a general symbol in the present invention denotes various specific substituents. These symbols can be any substituent, are not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.
The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, half-yl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, Sulfo-oxo (Sulfo-oxo), or thiol groups as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.
Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically mentioned in the present invention by identifying specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not refer to the specific term such as "alkyl alcohol" or the like at the same time.
This practice is also applicable to the other groups described in the present invention. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety may be otherwise specifically identified in the present invention; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl group may be, for example, "enol" and the like. Likewise, practice of using general terms such as "cycloalkyl" and specific terms such as "alkylcycloalkyl" is not intended to imply that the general terms do not also encompass the specific terms.
The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring made up of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" in which at least one ring carbon atom is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, or thiol groups as described herein.
The terms "alkoxy" and "alkoxy group," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OR1Wherein R is1Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether such as-OR1—OR2OR-OR1—(OR2)a—OR3Wherein "a" is an integer of 1 to 200, and R1,R2And R3Each independently is an alkyl group, a cycloalkyl group, or a combination thereof.
The term "alkenyl" as used herein is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R)1R2)C＝C(R3R4) Intended to include both the E and Z isomers. This can be presumed in the structural formula of the present invention in which an asymmetric olefin is present, or it can be explicitly represented by the bond symbol C ═ C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "cycloalkenyl" as used herein is a non-aromatic, carbon-based ring, consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, i.e., C ═ C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.
The term "alkynyl" as used herein is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.
The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group that contains an aromatic group, which does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde groups, amino, carboxylic acid groups, ester groups, ether groups, halogens, hydroxyl, ketone groups, azido, nitro, silyl, thio-oxo groups, or mercapto groups as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or two aryl groups connected via one or more carbon-carbon bonds, as in biphenyl.
The term "amine" or "amino" as used herein is defined by the formula-NR1R2Is represented by the formula (I) in which R1And R2Can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.
The term "alkylamino" as used herein is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.
The term "dialkylamino" as used herein, is defined by the formula-N (_ alkyl)2Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.
The term "ether" as used herein is defined by the formula R1OR2Is represented by, wherein R is1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is of the formula (R) — (R)1O-R2O)a-represents wherein R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine and iodine.
The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl and 1,3, 4-oxadiazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1,2,4, 5-tetrazinyl, tetrazolyl including 1,2,3, 4-tetrazolyl and 1,2,4, 5-tetrazolyl, thiadiazolyl including 1,2, 3-thiadiazolyl, 1,2, 5-thiadiazolyl and 1,3, 4-thiadiazolyl, thiazolyl, thienyl, thiadiazolyl including 1,3, 5-triazinyl and 1, triazinyl groups of 2, 4-triazinyl groups, triazolyl groups including 1,2, 3-triazolyl groups and 1,3, 4-triazolyl groups, and the like.
The term "ketone" as used herein is defined by the formula R1C(O)R2Is represented by the formula (I) in which R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "nitro" as used herein refers to the formula-NO2And (4) showing.
The term "nitrile" as used herein is represented by the formula — CN.
The term "silyl" as used herein, is defined by the formula-SiR1R2R3Is represented by the formula (I) in which R1,R2And R3And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "thio-oxo" as used herein is defined by the formula-S (O) R1,—S(O)2R1,—OS(O)2R1or-OS (O)2OR1Is represented by the formula (I) in which R1May be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the present specification, it is intended that,"S (O)" is a shorthand form of S ═ O. The term "sulfonyl", as used herein, refers to a compound of the formula-S (O)2R1A thio-oxo group of the formula, wherein R1Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "mock" as used herein is defined by the formula R1S(O)2R2Table in which R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein is defined by the formula R1S(O)R2Is represented by, wherein R is1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "mercapto" as used herein is represented by the formula — SH.
"R" used in the present invention1,”“R2,”“R3,”“Rn"(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R1Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendent (i.e., attached) to the second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.
The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.
The structure of the compound can be represented by the following formula:
it is understood to be equivalent to the following formula:
where n is typically an integer. Namely, RaIs understood to mean five individual substituents Ra(1),Ra(2),Ra(3),Ra(4),Ra (5). By "individual substituents" is meant each RaThe substituents may be independently defined. For example, if in one instance Ra(1)Is halogen, then in this case Ra(2)Not necessarily halogen.
R is referred to several times in the chemical structures and parts disclosed and described in this specification1,R2,R3,R4,R5,R6And the like. In the specification, R1,R2,R3,R4,R5,R6Etc. are each applicable to the citation of R1,R2,R3,R4,R5,R6Etc., unless otherwise specified.
The invention has the following advantages and beneficial effects:
the application discloses an organic luminescent or thermal-induced delayed fluorescence material based on a nitrogen difluoride-boron-oxygen heterocyclic acceptor. The organic luminescent material takes a high electrophilic nitrogen difluoride-boron-oxygen heterocyclic structure unit as an acceptor, and can form a luminescent material which is easy to regulate and control in luminescent color and high in quantum efficiency by combining different donors. The material can also avoid the use of rare metals, and has great application prospect in the field of OLED materials.
(1) The boron atoms in the material are in a high electron deficiency structure and have strong electron-withdrawing property; in addition, two fluorine atoms with strong electronegativity are linked to the boron atom, so that the electron-withdrawing capability of the boron atom can be further enhanced; the bond energy of boron-fluorine bond is high, and nitrogen and oxygen are bonded with boron respectively, so that the structure is stable; thus, the nitrogen difluoride-boron-oxa structure is a good acceptor unit.
(2) The excited state energy level of the material can be adjusted by adjusting and controlling the electron donating capability of the material structure or the donor, so that the luminous color of the material molecule can be conveniently adjusted and controlled.
(3) The luminescent material has simple molecular structure and is easy to synthesize and prepare.
Drawings
FIG. 1 is a spectrum of an emission spectrum of a toluene solution of a luminescent material NOBF2-1 at room temperature. The maximum emission wavelength is 438nm, and the material is a deep blue light emitting material.
FIG. 2 is a spectrum of an emission spectrum of a toluene solution of the luminescent material NOBF2-16 at room temperature. The maximum emission wavelength is 469nm, and the material is sky blue light emitting material.
FIG. 3 is a spectrum of an emission spectrum of a toluene solution of the luminescent material NOBF2-18 at room temperature. The maximum emission wavelength is 508nm, and the fluorescent material is green luminescent material.
FIG. 4 is a comparison of emission spectra of toluene solutions of luminescent materials NOBF2-1, NOBF2-16, and NOBF2-18 at room temperature.
Detailed Description
The following examples, which are merely exemplary of the present disclosure and are not intended to limit the scope thereof, provide those of ordinary skill in the art with a description of how to make and evaluate the compounds described herein and their OLED devices. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise specified, temperature is in units of ° c or at ambient temperature, and pressure is at or near atmospheric pressure.
The methods described in this example for the preparation of the disclosed compounds described herein are one of many and many others are possible and are not intended to limit the scope of the present application. Thus, one skilled in the art to which this disclosure pertains can readily modify the methods described or utilize different methods to prepare one or more of the disclosed compounds. The following methods are exemplary only, and the temperature, catalyst, concentration, reactant composition, and other process conditions may be varied, and one skilled in the art to which this disclosure pertains may readily select appropriate reactants and conditions for the preparation of the desired compound.
The organic luminescent or thermal induced delayed fluorescence material containing the nitrogen difluoride-boron-oxapolycyclic acceptor structural unit can be prepared according to the following method:
performed on a Varian Liquid State NMR instrument1H and13c NMR spectrum test. The solvent is CDCl3Or DMSO-d6. If tetramethylsilane is an internal standard in the solvent, reference is made to tetramethylsilane (δ 0.00 ppm); otherwise, if CDCl is used3Is a solvent, and is prepared by mixing the components,1chemical shifts of H NMR spectra were referenced to residual solvent (δ 7.26ppm),13chemical shifts of C NMR spectra were referenced to residual solvent (δ 77.00 ppm); if DMSO-d is used6Is a solvent, and is prepared by mixing the components,1chemical shift of H NMR spectrum is compared with residual solvent H2O(δ＝3.33ppm)，13Chemical shift of C NMR spectrum is compared with that of residual solvent DMSO-d6(δ 39.52 ppm). The nuclear magnetic data in the examples are explained using the following abbreviations (or combinations thereof)1Multiplicity of H NMR: s is singleplex, d is doublet, t is triplet, q is quartet, p is quintuple, m is multiplet, br is wide.
Preparation examples
Example 1: synthesis of luminescent Material NOBF2-1
Synthesis of intermediate 1: to a 250mL dry three-necked flask equipped with a magnetic rotor and a condenser were added 2, 4-dibromopyridine (15.72g,66.40mmol,1.0 eq.), 2-methoxyphenylboronic acid (11.10g,73.01mmol,1.1 eq.), Pd (PPh)3)4(2.30g,1.99mmol,3mol％),Na2CO3(21.11g,199.20mmol,3.0 eq.) nitrogen was purged three times. Tetrahydrofuran (120mL) and water (30mL) were added under nitrogen. The mixture was stirred in an oil bath at 85 ℃ for 48 hours, monitored by thin layer chromatography until the reaction of the starting materials was complete, and cooled to room temperature. The reaction mixture was extracted with ethyl acetate (50 mL. times.3), and the organic phases were combined and washed with anhydrous Na2SO4And (5) drying. Filtering, distilling under reduced pressure to remove the solvent, separating and purifying the crude product by using a silica gel chromatographic column, wherein the eluent is petroleum ether/ethyl acetate which is 20:1, and obtaining 16.43g of intermediate 1 light yellow liquid with the yield of 94%. Directly used for the next reaction.1H NMR(500MHz,DMSO-d6):δ3.85(s,3H),7.07(t,J＝7.5Hz,1H),7.17(d,J＝8.0Hz,1H),7.44(t,J＝7.5Hz,1H),7.60(d,J＝5.0Hz,1H),7.75(d,J＝8.0Hz,1H),8.06(s,1H),8.55(d,J＝5.5Hz,1H).
Synthesis of intermediate methoxy ether OCH 3-1: to a dry Schlenk tube were added in sequence intermediate 1(211mg,0.8mmol,1.0 equiv.), carbazole (0.96mmol,160.5mg,1.2 equiv.), Pd2(dba)3(14.7mg,0.02mmol,2.5 mol%), phosphine ligand L1(9.6mg,0.03mmol,3.75 mol%), sodium tert-butoxide (153.8mg,1.6mmol,2.0 equiv.). Then, nitrogen was purged three times, toluene (1mL) and dioxane (1mL) were added by injection, and the reaction was carried out at 95 ℃ for 27 hours. And (5) monitoring by thin-layer chromatography until the reaction of the raw materials is finished, and cooling to room temperature. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate 5:1-3:1 as eluent, to give 277mg of a pale yellow solid in 99% yield.1H NMR(500MHz,DMSO-d6):δ3.93(s,3H),7.13(td,J＝7.5,1.0Hz,1H),7.21(d,J＝8.0Hz,1H),7.36-7.39(m,2H),7.45-7.49(m,1H),7.54(td,J＝7.5,1.0Hz,2H),7.71(dd,J＝5.0,1.0Hz,1H),7.75(d,J＝8.5Hz,2H),7.92(dd,J＝7.5,2.0Hz,1H),8.17(d,J＝2.0Hz,1H),8.29(d,J＝7.5Hz,2H),8.91(d,J＝5.0Hz,1H)。
And (3) synthesizing an intermediate phenol OH-1: in a 25mL one-neck flask were added OCH3-1(277mg), acetic acid (2mL) and hydrobromic acid (2 mL; 48% strength), and the mixture was refluxed at 120 ℃ for 24 hours, monitored by thin layer chromatography until the starting material was reacted and cooled to room temperature. The solvent was removed under reduced pressure, a small amount of water was added, a sodium carbonate solution was added dropwise until no bubbling occurred, and filtration and drying were carried out to obtain 258mg of a pale yellow solid, with a yield of 96%. Directly used for the next reaction.
Synthesis of luminescent Material NOBF 2-1: a25 mL one-necked flask was charged with the intermediate phenol OH-1(258mg) obtained above, purged with nitrogen three times, and then dichloromethane (8mL), triethylamine (1.5mL) and boron trifluoride etherate (1.5mL) were injected. The reaction was then stirred at room temperature for 72 hours and, after completion of the reaction of the starting materials as monitored by thin layer chromatography, cooled to room temperature. Removing the solvent under reduced pressure, separating and purifying the crude product by using a silica gel chromatographic column, eluting the eluent: petroleum ether/ethyl acetate 5:1 gave 149mg of a yellow solid in 50% yield.1H NMR(500MHz,DMSO-d6):δ7.10-7.15(m,2H),7.42-7.46(m,2H),7.53-7.59(m,3H),7.89(d,J＝8.5Hz,2H),8.19(dd,J＝6.5,2.0Hz,1H),8.29-8.33(m,3H),8.87-8.90(m,2H)。
The emission spectrum of the toluene solution of luminescent material NOBF2-1 at room temperature is shown in figure 1. The maximum emission wavelength is 438nm, and the material is a deep blue light emitting material.
Example 2: synthesis of luminescent Material NOBF2-16
Synthesis of intermediate methoxy ether OCH 3-16: magnetitum, intermediate 1(900mg,3.4mmol,1.0 equiv.), diphenylamine (692mg,4.1mmol,1.2 equiv.), Pd were added to a dry Schlenk tube2(dba)3(62.0mg,0.068mmol,2 mol%), phosphine ligand L1(40mg,0.136mmol,4 mol%), sodium tert-butoxide (654mg,6.8mmol,2.0 equiv.). Then theThe nitrogen was purged three times, toluene (1mL) and dioxane (1mL) were added by injection, and then reacted at 95 ℃ for 27 hours. And (5) monitoring by thin-layer chromatography until the reaction of the raw materials is finished, and cooling to room temperature. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the crude product by using a silica gel chromatographic column, and eluting the eluent: oil ether: ethyl acetate 10:1-5:1 gave 588mg of yellow viscous liquid in 49% yield.1H NMR(500MHz,DMSO-d6):δ3.66(s,3H),6.55(dd,J＝6.0,2.5Hz,1H),6.99-7.04(m,2H),7.22(d,J＝2.0Hz,1H),7.25-7.27(m,6H),7.32-7.35(m,1H),7.43-7.47(m,4H),7.74(dd,J＝7.5,1.5Hz,1H),8.27(d,J＝5.5Hz,1H)。
And (3) synthesizing an intermediate phenol OH-16: in a 25mL single-necked flask was charged OCH3-16(588mg,1.67mmol), nitrogen was purged three times, dichloromethane (10mL) was injected, and BBr was added dropwise3(646. mu.l). Then stirring and reacting for 3 days at room temperature, adding a small amount of dichloromethane for dilution, removing the solvent under reduced pressure, separating and purifying a crude product by using a silica gel chromatographic column, and eluting a eluent: petroleum ether/ethyl acetate 10:1-5:1 gave 437mg of a yellow solid in 67% yield.1H NMR(500MHz,DMSO-d6):δ6.58(dd,J＝6.0,2.5Hz,1H),6.77-6.81(m,1H),6.85(dd,J＝8.0,1.0Hz,1H),7.16(d,J＝2.5Hz,1H),7.21-7.25(m,1H),7.31-7.35(m,7H),7.47-7.51(m,4H),8.23(d,J＝6.0Hz,1H),14.53(s,1H)。
Synthesis of luminescent material NOBF 2-16: a25 mL one-neck flask was charged with the intermediate phenolic OH-16(437mg, 1.12mmol,1.0 eq.) obtained above, purged with nitrogen three times, and then injected with dichloromethane (10mL), triethylamine (3.2mL) and boron trifluoride etherate (2.8 mL). The reaction was then stirred at room temperature for 3 days, monitored by thin layer chromatography until the starting material had reacted, and cooled to room temperature. Removing the solvent under reduced pressure, separating and purifying the crude product by using a silica gel chromatographic column, eluting the eluent: petroleum ether/ethyl acetate 5:1-3:1 gave 407mg of a yellow-green solid in 94% yield.1H NMR(500MHz,DMSO-d6):δ6.72(dd,J＝7.0,2.5Hz,1H),6.94-6.97(m,1H),6.99(d,J＝7.5Hz,1H),7.07(d,J＝2.5Hz,1H),7.41-7.46(m,4H),7.51-7.53(m,4H),7.56-7.59(m,4H),8.25(d,J＝7.0Hz,1H)。
The emission spectrum of the toluene solution of luminescent material NOBF2-16 at room temperature is shown in figure 1. The maximum emission wavelength is 469nm, and the material is sky blue light emitting material.
Example 3: synthesis of luminescent Material NOBF2-18
Synthesis of intermediate methoxy ether OCH 3-18: to a dry Schlenk tube were added in order intermediate 1(190.2mg,0.72mmol,1.2 equiv.), bis (biphenylyl) amine (192.9mg,0.6mmol,1.0 equiv.), Pd2(dba)3(14.7mg,0.012mmol,2 mol%), phosphine ligand L1(7.2mg,0.024mmol,4 mol%), sodium tert-butoxide (115.3mg,1.2mmol,2.0 equiv.). Then, nitrogen was purged three times, toluene (1mL) and dioxane (1mL) were added by injection, and then reacted at 95 ℃ for 24 hours. And (5) monitoring by thin-layer chromatography until the reaction of the raw materials is finished, and cooling to room temperature. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate 5:1-3:1 as eluent gave 156mg of a pale yellow solid in 52% yield.1H NMR(500MHz,DMSO-d6):δ3.70(s,3H),5.76(s,1H),6.72(dd,J＝5.5,2.5Hz,1H),7.01-7.05(m,2H),7.33-7.39(m,7H),7.46-7.50(m,4H),7.69-7.71(m,4H),7.76-7.79(m,5H),8.34(d,J＝5.5Hz,1H)。
And (3) synthesizing an intermediate phenol OH-18: in a 25mL one-neck flask were added OCH3-18(155mg), acetic acid (1mL) and hydrobromic acid (2 mL; 48% strength), and the mixture was refluxed at 120 ℃ for 24 hours, monitored by thin layer chromatography until the starting material was reacted, and cooled to room temperature. The solvent was removed under reduced pressure, a small amount of water was added, a sodium carbonate solution was added dropwise until no bubbling occurred, and filtration and drying were carried out to obtain 87mg of a pale yellow solid in a yield of 60%. Directly used for the next reaction.
Synthesis of luminescent material NOBF 2-18: a25 mL one-necked flask was charged with the intermediate phenol OH-18(87mg) obtained above, purged with nitrogen three times, and then dichloromethane (8mL), triethylamine (1.2mL) and boron trifluoride etherate (1.2mL) were injected. The reaction was then stirred at room temperature for 3 days, monitored by thin layer chromatography until the starting material had reacted, and cooled to room temperature. Removing solvent under reduced pressure, separating and purifying the crude product with silica gel chromatographic column, and elutingPreparation: petroleum ether/ethyl acetate 5:1 gave 25mg of a yellow solid in 25.7% yield.1H NMR(500MHz,DMSO-d6):δ6.89(dd,J＝7.0,2.5Hz,1H),6.99(d,J＝8.5Hz,1H),7.39-7.42(m,3H),7.49-7.52(m,4H),7.57-7.63(m,5H),7.74-7.75(m,3H),7.75-7.76(m,2H),7.80(d,J＝2.0Hz,1H),7.86-7.88(m,4H),8.31(d,J＝7.5Hz,1H)。
The emission spectrum of the toluene solution of luminescent material NOBF2-18 at room temperature is shown in figure 1. The maximum emission wavelength is 508nm, and the fluorescent material is green luminescent material.
Performance evaluation examples
The complexes prepared in the above examples of the invention were photophysically analyzed as follows:
and (3) testing conditions are as follows: in the room temperature emission spectrum, all samples were toluene (chromatographic grade) dilute solutions (10)-5-10-6M). The luminescent quantum efficiency (PLQY) was measured for a 10 wt% doped DEPEO film sample of the luminescent material. Wherein the DEPEO structure is shown in the following figure.
The following table summarizes the photophysical properties of the three luminescent materials in FIGS. 1 to 4.
TABLE 1 photophysical Properties of the luminescent materials
| Luminescent material | Peak/nm | Quantum efficiency |
| NOBF2-1 | 438 (deep blue light) | 80％ |
| NOBF2-16 | 469 (sky blue light) | 75％ |
| NOBF2-18 | 508 (Green light) | 73％ |
Note: peak refers to the strongest emission Peak of the emission spectrum of the luminescent material in toluene solution at room temperature.
As can be seen from the accompanying figures 1-4 and table 1: the luminescent color of the material is easy to regulate and control: under the condition of keeping the structure of the receptor unchanged, the regulation and control of the luminescent color of the material from deep blue light to green light can be realized only by simply regulating the structure of the donor; the quantum efficiency of the luminescent material is high and is more than 70 percent; the organic light emitting diode is simple in structure and easy to synthesize and prepare, the properties are beneficial to the application of the organic light emitting diode as a doped light emitting body in an OLED device, an effective way is provided for solving the problem of the existing short blue light emitting material, and the development of the field is greatly promoted.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention.
Claims (6)
1. An organic luminescent or thermal induced delayed fluorescence material containing a nitrogen difluoride-boron-oxapolycyclic acceptor structural unit as shown in a formula (1):
wherein,
Raand RbEach independently is hydrogen, deuterium, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 cycloalkyl, C1-C24 ether, C1-C24 heterocyclyl, C1-C24 aryl, C1-C24 aryloxy, halogen, mono-or dialkylamino, mono-or diarylamino, cyano, or a combination thereof;
m and n are respectively a substituent RaAnd RbM is an integer of 0 to 4, n is an integer of 0 to 3;
the donor D may be one of the following structures:
wherein,
R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14and R15Each independently hydrogen, deuterium, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 cycloalkyl, C1-C24 ether, C1-C24 heterocyclic group, C1-C24 aryl, C1-C24 aryloxy, halogen, silicon group, mono-or dialkylamino group, mono-or diarylamino group, cyano group or a combination thereof, wherein two adjacent substituents can be fused to form a ring;
wherein o, p, q, R, s, t, u, v, w, x, y and z are substituents R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14And R15O and p are each independently an integer of 0 to 5; q, r, s, t, u, v, w, x, y and z are each independently integers of 0 to 4.
2. The organic luminescent or thermally delayed fluorescent material according to claim 1, characterized in that: the substituent R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14And R15Each independently hydrogen, deuterium, alkyl of C1-C24, alkoxy of C1-C24, cycloalkyl of C1-C24, heterocyclic of C1-C24, aryl of C1-C24, aryloxy of C1-C24, mono-or dialkylamino, mono-or diarylamino, cyano.
3. The organic luminescent or thermally delayed fluorescent material according to claim 1, characterized in that: the organic luminescent or thermal induced delayed fluorescence material is selected from one of the following materials:
4. use of the organic light-emitting or thermally delayed fluorescent material according to any of claims 1 to 2 as a functional material in a light-emitting device, including an organic light-emitting diode, a lighting device.
5. A light-emitting device comprising a first electrode, a second electrode, and at least one organic thin film between the anode and the cathode, wherein the organic thin film contains the organic light-emitting or thermally delayed fluorescent material according to any one of claims 1 to 3.
6. The organic light-emitting device according to claim 4, wherein the organic light-emitting or thermally delayed fluorescent material comprising the structural unit of the nitrogen difluoride-boron-oxapolycyclic acceptor is used as a light-emitting material, a host material or other functional layer materials in the organic light-emitting device.
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