CN113234098B - 一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 - Google Patents
一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 Download PDFInfo
- Publication number
- CN113234098B CN113234098B CN202110545959.3A CN202110545959A CN113234098B CN 113234098 B CN113234098 B CN 113234098B CN 202110545959 A CN202110545959 A CN 202110545959A CN 113234098 B CN113234098 B CN 113234098B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- fluorescent material
- thermally
- organic light
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 91
- 230000003111 delayed effect Effects 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 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
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 claims description 9
- 125000003367 polycyclic group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 239000010409 thin film Substances 0.000 claims 2
- 239000002346 layers by function Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 description 42
- -1 nitrogen-boron-oxygen polycyclic aromatic compound Chemical class 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 125000003118 aryl group Chemical group 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 125000000753 cycloalkyl group Chemical group 0.000 description 27
- 125000000392 cycloalkenyl group Chemical group 0.000 description 20
- 125000001072 heteroaryl group Chemical group 0.000 description 18
- 125000003545 alkoxy group Chemical group 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 9
- 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
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 125000003396 thiol group Chemical class [H]S* 0.000 description 7
- 125000000464 thioxo group Chemical group 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
- 125000004429 atom Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002994 raw material Substances 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000007858 starting material 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
- 150000001540 azides Chemical class 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 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
- 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
- 238000010926 purge Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 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
- 239000004215 Carbon black (E152) Substances 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic 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
- 150000005347 biaryls Chemical group 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
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 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
- 125000004986 diarylamino group Chemical group 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
- 238000001914 filtration Methods 0.000 description 2
- 229920002457 flexible plastic Polymers 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
- 239000011521 glass Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 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
- 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
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 238000004458 analytical method Methods 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
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 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
- 230000002950 deficient Effects 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
- 230000005684 electric field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 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
- 150000002085 enols Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 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
- 150000002430 hydrocarbons Chemical group 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
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl 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
- 150000002739 metals Chemical class 0.000 description 1
- 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
- 150000002829 nitrogen Chemical class 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
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 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
- 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 239000000758 substrate Substances 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
- 125000001113 thiadiazolyl 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
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
Images
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
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一类含有二氟化氮‑硼‑氧杂环受体的有机发光或热致延迟荧光材料及其应用。该类有机发光材料以高亲电性的二氟化氮‑硼‑氧杂环结构单元为受体,结合不同的给体,可形成一类发光颜色易调、量子效率高的热致延迟荧光材料,在OLED材料领域有巨大的应用前景。
Description
技术领域
本发明属于有机发光材料领域,特别涉及一类含有二氟化氮-硼-氧杂多环受体结构单元的有机发光或热致延迟荧光材料,可用于OLED显示和照明领域。
背景技术
有机发光二极管(OLED,Organic Light-Emitting Diode)又被称作有机发光器件(Organic Light-Emitting Device)或有机电致发光器件(Organic ElectroluminescentDevice)。有机电致发光是指在顺向偏压电场的作用下有机小分子、金属有机配合物分子或聚合物分子发光材料将电能直接转化为光能的一种发光现象。OLED是自主发光,无需背光源,节能;还具有响应速度快、驱动电压低、发光效率和分辨率高、视角广、对比度高等特点;此外它能以廉价的玻璃、金属甚至柔性的塑料为基板,因此还具有成本低、生产工艺简单、可进行大面积生产等优点,已成为新一代的全彩显示和照明技术,在手机、电脑、电视、数码相机、GPS、及可弯曲和折叠等电子产品以及照明领域具有广阔而巨大的应用前景,受到学术界和工业界的广泛重视。
早期器件所采用的发光材料主要为第一代有机小分子荧光材料,而自旋统计量子学表明荧光材料的电致发光理论内部量子效率仅为25%,限制了其在OLED中的应用。1998年美国的Forrest教授和Thompson教授实现了室温下金属铂有机配合物分子的磷光电致发光现象(Nature,1998,395,151);同年,中国的马於光教授和支志明教授亦报道了金属锇配合物的磷光电致发光(Synth.Met.,1998,94,245),均为第二代磷光材料。此类材料是利用重金属原子的强自旋轨道耦合以有效促进电子由单线态到三线态的系间蹿越,从而OLED器件可以充分利用电激发所产生的所有单线态和三线态激子(exciton),使发光材料的理论内部量子效率可达到100%。2009年日本的Adachi教授发展了新型的第三代发光材料,即热致延迟荧光材料(TADF,thermally activated delayed fluorescence),通过合理的结构设计,得到具有很小的单线态-三线态能系(ΔEST)有机分子,在周围环境中热量的激发下,即可实现激子由三线态到单线态的系间蹿越,从而充分利用所有激子,理论上亦可达到100%的内部量子效率(Adv.Mater.,2009,21,4802),且掺杂此类材料的器件效率亦达到了磷光器件的性能(Nat.Photonics,2014,8,326)。自此,此类材料得到了人们的广泛关注。
虽然金属有机磷光材料已取得了长足的发展,红光和绿光金属铱配合物磷光材料已实现在商业化电子产品中的应用,但是在量子效率和稳定性方面皆可满足商业化需求的金属磷光材料还极其有限,尤其是蓝光磷光材料一直难以达到商业应用的要求;此外,稀有重金属材料极为昂贵,且资源有限,是其严重不足之处。因此急需发展新的纯有机发光材料,尤其是高效的热致延迟荧光材料来解决上述问题;同时,新型高效的蓝光热致延迟荧光材料的设计和开发亦是OLED领域的重大问题。
发明内容
本发明的目的在于提供一类基于给体-受体的氮硼氧杂多环芳烃化合物发光材料或热致延迟荧光材料,该类材料可用于OLED显示和照明领域。
本发明提供了一类含有二氟化氮-硼-氧杂多环受体结构单元的如式(1)所示的有机发光或热致延迟荧光材料:
其中,
氮-硼-氧依次相连成键,且硼和两个氟原子相连成键形成稳定的二氟化硼结构;
Ra和Rb各自独立地为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的醚、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、卤素、单或二烷基氨基、单或二芳基氨基、氰基或其组合;
m、n分别为取代基Ra和Rb的个数,m为0-4的整数,n为0-3的整数;
给体D可以为以下结构之一:
其中,
R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14和R15各自独立为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的醚、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、卤素、硅基、单或二烷基氨基、单或二芳基氨基、氰基或其组合,其中相邻的两个取代基可以稠合成环;
o、p、q、r、s、t、u、v、w、x、y和z分别为取代基R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14、R15的个数,o和p各自独立为0-5的整数;q、r、s、t、u、v、w、x、y和z各自独立为0-4的整数。
进一步,优选的,所述的取代基R1、R2、R3、R4、R7、R8、R10、R11、R12、R13、R14和R15各自独立为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、单或二烷基氨基、单或二芳基氨基、氰基。
再进一步,在本发明的一些具体实施方式中,含有一类含有二氟化氮-硼-氧杂多环受体结构单元的有机发光或热致延迟荧光材料具有选自如下之一的结构:
在本发明所述的含有二氟化氮-硼-氧杂多环受体结构单元的有机发光或热致延迟荧光材料为电中性。
本发明使用的连接原子能够连接两个基团,例如,N和C基团。该连接原子能够任选地(如果价键允许)具有其他附接的化学部分。例如,在一方面,氧不会具有任何其它的化学基团附接,因为一旦键合至两个原子(例如,N或C)价键已经被满足。相反,当碳是连接原子时,两个另外的化学部分能够附接至该碳原子。合适的化学部分包括但不限于氢,羟基,烷基,烷氧基,=O,卤素,硝基,胺,酰胺,硫醇基,芳基,杂芳基,环烷基,和杂环基。
本发明使用的术语“环状结构”或类似术语是指任何环状化学结构,其包括但不限于芳基,杂芳基,环烷基,环烯基,杂环基,卡宾,和N-杂环卡宾。
本发明使用的术语“取代的”预期包含有机化合物的所有允许的取代基。在宽的方面,允许的取代基包括有机化合物的非环和环状、支化的和非支化的、碳环的和杂环的,和芳族和非芳族取代基。说明性的取代基包括,例如,以下描述的那些。对于合适的有机化合物来说,允许的取代基可为一个或多个,相同或者不同。对于本发明的目的而言,杂原子(例如氮)能够具有氢取代基和/或本发明所述的有机化合物的任何允许的取代基,其满足该杂原子的价键。本公开不意图以任何方式用有机化合物允许的取代基来进行任何限制。同样,术语“取代”或“取代有”包含隐含条件是这种取代符合取代的原子和该取代基的允许的价键,和该取代导致稳定的化合物(例如,不会自发地进行转化(例如通过重排、环化、消去等)的化合物)。也预期,在某些方面,除非明确地相反地指出,否则,单独的取代基能够进一步任选地是取代的(即,进一步是取代或未取代的)。
在定义各种术语时,“R1”、“R2”、“R3”和“R4”在本发明中用作总的符号来表示各种具体的取代基。这些符号能够是任何取代基,不限于本发明披露的那些,和当将他们在一种情况下限定为某些取代基时,他们在其它情况下可限定为一些其它的取代基。
本发明使用的术语“烷基”是支化的或未支化的1至24个碳原子的饱和的烃基,例如甲基,乙基,正丙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,正戊基,异戊基,仲戊基,新戊基,己基,庚基,半基,壬基,癸基,十二烷基,十四烷基,十六烷基,二十烷基,二十四烷基等。该烷基可为环状或非环的。该烷基可为支化或者非支化的。该烷基也可为取代或未取代的。例如,该烷基可取代有一个或多个基团,包括但不限于本发明所述的任选取代的烷基,环烷基,烷氧基,氨基,醚,卤素,羟基,硝基,甲硅烷基,硫-氧代(Sulfo-oxo),或硫醇基。“低级烷基”基团是含有1至6个(例如1至4个)碳原子的烷基。
在整个说明书中,“烷基”通常用于同时指代未取代烷基和取代烷基;但是,取代烷基也在本发明中通过确定烷基上的具体的取代基来具体地提及。例如,术语“卤化的烷基”或者“卤代烷基”具体地是指取代有一个或多个卤素(例如,氟,氯,溴,或碘的)烷基。术语“烷氧基烷基”具体地是指取代有一个或多个烷氧基的烷基,如下所述。术语“烷基氨基”具体地是指取代有一个或多个氨基的烷基,如下所述,等。当在一种情况中使用“烷基”而在另一情况中使用具体的术语如“烷基醇”时,不意味着暗示该术语“烷基”不同时指代具体的术语如“烷基醇”等。
本实践也用于本发明所述的其它组。也即,当术语如“环烷基”同时指代未取代的和取代的环烷基部分时,该取代的部分可另外具体地在本发明中确定;例如,具体取代的环烷基可称为例如“烷基环烷基”。类似的,取代的烷氧基可具体地称为例如“卤化的烷氧基”,具体的取代烯基可为例如“烯醇”等。同样地,使用总的术语如“环烷基”和具体的术语如“烷基环烷基”的实践不意图暗示该总术语不同时包含该具体术语。
本发明使用的术语“环烷基”是由至少三个碳原子构成的非芳族基于碳的环。环烷基的实例包括但不限于环丙基,环丁基,环戊基,环己基,环壬基,等。术语“杂环烷基”是一类如上定义的环烷基,并且包含在术语“环烷基”的含义中,其中至少一个环碳原子被杂原子例如但不限于氮,氧,硫,或磷取代。该环烷基和杂环烷基可为取代或未取代的。该环烷基和杂环烷基可取代有一个或多个基团,包括但不限于如本发明所述的烷基,环烷基,烷氧基,氨基,醚,卤素,羟基,硝基,甲硅烷基,硫-氧代(sulfo-oxo),或硫醇基。
术语“烷氧基”和“烷氧基基团”,其用在本发明中用来指代通过醚连接基键合的烷基或环烷基;也即,“烷氧基”可定义为—OR1,其中R1是如上定义的烷基或环烷基。“烷氧基”也包含刚刚描述的烷氧基的聚合物;也即,烷氧基可为聚醚如—OR1—OR2或者—OR1—(OR2)a—OR3,其中“a”是整数1至200,而R1,R2,和R3各自独立地为烷基,环烷基,或其组合。
本发明使用的术语“烯基”是2至24个碳原子的烃基,其结构式含有至少一个碳-碳双键。不对称结构例如(R1R2)C=C(R3R4)意图包含E和Z异构体。这可推定在本发明的结构式中,其中存在不对称烯烃,或者它可通过键符号C=C明确表示。该烯基可取代有一个或多个基团,包括但不限于本发明所述的烷基,环烷基,烷氧基,烯基,环烯基,炔基,环炔基,芳基,杂芳基,醛,氨基,羧酸,酯,醚,卤素,羟基,酮,叠氮基,硝基,甲硅烷基,硫基-氧代(sulfo-oxo),或硫醇基。
本发明使用的术语“环烯基”是非芳族的基于碳的环,其由至少3个碳原子构成,并且含有至少一个碳碳双键,即,C=C。环烯基的实例包括但不限于环丙烯基,环丁烯基,环戊烯基,环戊二烯基,环己烯基,环己二烯基,降冰片烯基,等。术语“杂环烯基”是一类如上定义的环烯基,并且包含在术语“环烯基”的含义中,其中该环的至少一个碳原子用杂原子例如但不限于氮、氧、硫、或磷取代。环烯基和杂环烯基可为取代或未取代的。该环烯基和杂环烯基可取代有一个或多个基团,包括但不限于本发明所述的烷基,环烷基,烷氧基,烯基,环烯基,炔基,环炔基,芳基,杂芳基,醛,氨基,羧酸,酯,醚,卤素,羟基,酮,叠氮基,硝基,甲硅烷基,硫基-氧代(sulfo-oxo),或硫醇基。
本发明使用的术语“炔基”是具有2至24个碳原子的烃基,其具有含有至少一个碳-碳三键的结构式。炔基可为未取代的或者取代有一个或者多个基团,所述基团包括但不限于本发明所述的烷基,环烷基,烷氧基,烯基,环烯基,炔基,环炔基,芳基,杂芳基,醛,氨基,羧酸,酯,醚,卤素,羟基,酮,叠氮基,硝基,甲硅烷基,硫基-氧代(sulfo-oxo),或硫醇基。
本发明使用的术语“芳基”是含有任何基于碳的芳族基团的基团,所述基于碳的芳族基团包括但不限于苯、萘、苯基、联苯、苯氧基苯等。术语“芳基”也包括“杂芳基”,其被定义为含有芳族基团的基团,所述芳族基团具有至少一个引入芳族基团的环内的杂原子。杂原子的实例包括但不限于氮、氧、硫,和磷。同样,术语“非杂芳基”(其也包括在术语“芳基”中)定义了含有芳族基团的基团,所述芳族基团不含杂原子。芳基可为取代或未取代的。芳基可取代有一个或者多个基团,所述基团包括但不限于本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基、杂芳基、醛基团、氨基、羧酸基团、酯基团、醚基团、卤素、羟基、酮基团、叠氮基、硝基、甲硅烷基、硫-氧代基团,或者巯基。术语“联芳基(biaryl)”是特定类型的芳基并且包含在“芳基”的定义中。联芳基是指经稠合的环结构结合在一起的两个芳基,如在萘中一样,或者经一个或者多个碳-碳键连接的两个芳基,如在联苯中一样。
本发明使用的术语“胺”或“氨基”通过式-NR1R2表示,其中R1和R2可以独立的从氢、烷基、环烷基,烯基,环烯基,炔基,环炔基,芳基或杂芳基中选择。
本发明使用的术语“烷基氨基”通过式-NH(-烷基)表示,其中烷基如本发明所述。代表性实例包括但不限于甲基氨基、乙基氨基、丙基氨基、异丙基氨基、丁基氨基、异丁基氨基、(仲丁基)氨基、(叔丁基)氨基、戊基氨基、异戊基氨基、(叔戊基)氨基、己基氨基等。
本发明使用的术语“二烷基氨基”通过式-N(_烷基)2表示,其中烷基如本发明所述。代表性实例包括但不限于二甲基氨基、二乙基氨基、二丙基氨基、二异丙基氨基、二丁基氨基、二异丁基氨基、二(仲丁基)氨基、二(叔丁基)氨基、二戊基氨基、二异戊基氨基、二(叔戊基)氨基、二己基氨基、N-乙基-N-甲基氨基、N-甲基-N-丙基氨基、N-乙基-N-丙基氨基等。
本发明使用的术语“醚”通过式R1OR2,表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。本发明使用的术语“聚醚”通过式—(R1O-R2O)a—表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基并且“a”为1至500的整数。聚醚基团的实例包括聚氧化乙烯、聚氧化丙烯,和聚氧化丁烯。
本发明使用的术语“卤素”是指卤素氟、氯、溴和碘。
本发明使用的术语“杂环基”是指单环的和多环的非芳族环系,并且本发明使用的“杂芳基”是指单环的和多环的芳族环系:其中环成员中的至少一个不为碳。该术语包括氮杂环丁烷基、二噁烷基、呋喃基、咪唑基、异噻唑基、异噁唑基、吗啉基、噁唑基、包括1,2,3-噁二唑基、1,2,5-噁二唑基和1,3,4-噁二唑基的噁唑基、哌嗪基、哌啶基、吡嗪基、吡唑基、哒嗪基、吡啶基、嘧啶基、吡咯基、吡咯烷基、四氢呋喃基、四氢吡喃基、包括1,2,4,5-四嗪基的四嗪基、包括1,2,3,4-四唑基和1,2,4,5-四唑基的四唑基、包括1,2,3-噻二唑基、1,2,5-噻二唑基和1,3,4-噻二唑基的噻二唑基、噻唑基、噻吩基、包括1,3,5-三嗪基和1,2,4-三嗪基的三嗪基、包括1,2,3-***基和1,3,4-***基的***基等。
本发明使用的术语“酮”通过式R1C(O)R2表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。
本发明使用的术语“硝基”通过式—NO2表示。
本发明使用的术语“腈”通过式—CN表示。
本发明使用的术语“甲硅烷基”通过式—SiR1R2R3表示,其中R1,R2和R3可独立地为氢或者本发明所述的烷基、环烷基、烷氧基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。
本发明使用的术语“硫-氧代基团”通过式—S(O)R1,—S(O)2R1,—OS(O)2R1或者—OS(O)2OR1表示,其中R1可为氢或者本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。在整个说明书中,“S(O)”为S=O的简写形式。本发明使用的术语“磺酰基”是指通过式—S(O)2R1表示的硫-氧代基团,其中R1可为烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。本发明使用的术语“讽”通过式R1S(O)2R2表不,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。本发明使用的术语“亚砜”通过式R1S(O)R2,表示,其中R1和R2可独立地为本发明所述的烷基、环烷基、烯基、环烯基、炔基、环炔基、芳基,或者杂芳基。
本发明使用的术语“巯基”通过式一SH表示。
本发明使用的“R1,”“R2,”“R3,”“Rn”(其中n为整数)可独立地具有上面列举的基团中的一个或者多个。例如,如果R1为直链烷基,那么烷基的一个氢原子可任选取代有羟基、烷氧基、烷基、卤素等。取决于选择的基团,第一基团可结合在第二基团内,或者可选择地,第一基团可悬挂(即,连接)至第二基团。例如,对于短语“包含氨基的烷基”,氨基可结合在烷基的主链内。可选择地,氨基可连接至烷基的主链。所选基团的性质将决定是否第一基团嵌入或者连接至第二基团。
本发明所述化合物可含有“任选取代的”部分。通常,术语“取代的”(无论在前面是否存在术语“任选”)意味着指出的部分的一个或者多个氢被适合的取代基替代。除非另作说明,否则“任选取代的”基团可在基团的每个可取代位置具有适合的取代基,以及当在任何给出的结构中超过一个位置可取代有超过一个选自指定基团的取代基时,在每个位置的取代基可相同或者不同。本发明设想的取代基组合优选为形成稳定的或者化学上可行的化合物的那些。在某些方面,除非清楚地相反指示,否则还涵盖的是,各个取代基可进一步任选被取代(即,进一步取代或未取代的)。
化合物的结构可通过下式表示:
其被理解为等同于下式:
其中n通常为整数。即,Ra被理解为表示五个单独的取代基Ra(1),Ra(2),Ra(3),Ra(4),Ra (5)。“单独的取代基”是指每个Ra取代基可独立地限定。例如,如果在一个情况中Ra(1)为卤素,那么在这种情况下Ra(2)不一定是卤素。
在本发明公开的和描述的化学结构和部分中数次提及R1,R2,R3,R4,R5,R6等。在说明书中R1,R2,R3,R4,R5,R6等的任何描述分别适用于引用R1,R2,R3,R4,R5,R6等的任何结构或者部分,除非另作说明。
本发明具有以下优点和有益效果:
本申请所述的一类基于二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料。该类有机发光材料以高亲电性的二氟化氮-硼-氧杂环结构单元为受体,结合不同的给体,可形成一类发光颜色极易调控且、量子效率高的发光材料。此类材料亦可避免稀有金属的使用,在OLED材料领域有巨大的应用前景。
(1)本申请所述的材料中的硼原子为高缺电子结构,具有很强的吸电子性质;此外,硼原子上联有两个电负性强的氟原子,可进一步增强硼原子的吸电子能力;并且硼-氟键键能高,且氮、氧分别和硼成键,结构稳定;因此,二氟化氮-硼-氧杂结构是很好的受体单元。
(2)可以通过调控材料结构或给体的供电子能力,从而调节材料的激发态能级,从而方便的调控材料分子的发光颜色。
(3)发光材料分子结构简单,易于合成制备。
附图说明
图1是发光材料NOBF2-1的甲苯溶液在室温下的发射光谱谱图。其最大发射波长在438nm,为深蓝光发光材料。
图2是发光材料NOBF2-16的甲苯溶液在室温下的发射光谱谱图。其最大发射波长在469nm,为天蓝光发光材料。
图3是发光材料NOBF2-18的甲苯溶液在室温下的发射光谱谱图。其最大发射波长在508nm,为绿光发光材料。
图4是发光材料NOBF2-1、NOBF2-16、NOBF2-18的甲苯溶液在室温下的发射光谱谱图比较。
具体实施方式
以下实施例向本领域普通技术人员提供如何制造和评价本发明描述的化合物及其OLED器件,所述实施例仅是本公开内容的示范且不圈定限制范围。尽管已经尽力确保关于数值(例如,量、温度等)的准确性,但是应当考虑一些误差和偏差。除非另外说明,否则温度是以℃为单位或者在环境温度下,且压力是在大气压下或附近。
本实施例中所叙述的用于本发明所描述的公开化合物的制备方法是众多方法中的一种,本发明申请公开化合物的制备方法尚有很多其他方法,本申请不圈定限制范围。因此,本公开内容所属领域的技术人员可容易地修改所叙述的方法或者利用不同的方法来制备所公开的化合物的一种或多种。下列方法仅是示例性的,温度、催化剂、浓度、反应物组成、以及其它工艺条件可改变,并且对于期望的化合物,本公开内容所属领域的技术人员可以容易的选择合适的反应物和条件进行制备。
本发明所述的含有二氟化氮-硼-氧杂多环受体结构单元的有机发光或热致延迟荧光材料可以按照如下方法进行制备:
在Varian Liquid State NMR仪器上进行1H和13C NMR图谱测试。溶剂为CDCl3或DMSO-d6。溶剂中如有内标四甲基硅烷,化学位移则参照四甲基硅烷(δ=0.00ppm);否则,若以CDCl3为溶剂,1H NMR图谱化学位移则参照残留溶剂(δ=7.26ppm),13C NMR图谱化学位移则参照残留溶剂(δ=77.00ppm);若以DMSO-d6为溶剂,1H NMR图谱化学位移则参照残留溶剂H2O(δ=3.33ppm),13C NMR图谱化学位移则参照残留溶剂DMSO-d6(δ=39.52ppm)。实施例中核磁数据使用下列缩写(或其组合)来解释1H NMR的多重性:s=单重,d=双重,t=三重,q=四重,p=五重,m=多重,br=宽。
制备实施例
实施例1:发光材料NOBF2-1的合成
中间体1的合成:向带有磁力转子和冷凝管的250mL干燥三口瓶中依次加入2,4-二溴吡啶(15.72g,66.40mmol,1.0当量),2-甲氧基苯硼酸(11.10g,73.01mmol,1.1当量),Pd(PPh3)4(2.30g,1.99mmol,3mol%),Na2CO3(21.11g,199.20mmol,3.0当量),抽换氮气三次。在氮气保护下加入四氢呋喃(120mL)和水(30mL)。混合物在85℃油浴中搅拌反应48小时,薄层色谱监测至原料反应完毕,冷却至室温。反应混合物用乙酸乙酯萃取(50mL×3),合并有机相,用无水Na2SO4干燥。过滤,减压蒸馏除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂为石油醚/乙酸乙酯=20:1,得到中间体1淡黄色液体16.43g,收率94%。直接用于下一步反应。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).
中间体甲氧基醚OCH3-1的合成:在干燥的Schlenk管中依次加入中间体1(211mg,0.8mmol,1.0当量)、咔唑(0.96mmol,160.5mg,1.2当量)、Pd2(dba)3(14.7mg,0.02mmol,2.5mol%)、膦配体L1(9.6mg,0.03mmol,3.75mol%)、叔丁醇钠(153.8mg,1.6mmol,2.0当量)。然后排换氮气三次,注射加入甲苯(1mL)和二氧六环(1mL),而后在95℃下反应27小时。薄层色谱监测至原料反应完毕,冷却至室温。减压蒸馏除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=5:1—3:1为洗脱剂,得到浅黄色固体277mg,,收率99%。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)。
中间体酚OH-1的合成:在25mL单口瓶中加入OCH3-1(277mg),乙酸(2mL)和氢溴酸(2mL;浓度48%),然后该混合物在120℃下回流24小时,薄层色谱监测至原料反应完毕,冷却至室温。减压除去溶剂,加入少量水,滴加碳酸钠溶液至不冒泡,过滤干燥得到淡黄色固体258mg,收率96%。直接用于下一步反应。
发光材料NOBF2-1的合成:在25mL单口瓶中加入上述得到的中间体酚OH-1(258mg),排换氮气三次后,注射加入二氯甲烷(8mL)、三乙胺(1.5mL)和三氟化硼***络合物(1.5mL)。然后在室温下搅拌反应72小时,薄层色谱监测至原料反应完毕,冷却至室温。减压除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=5:1得到黄色固体149mg,收率50%。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)。
发光材料NOBF2-1的甲苯溶液在室温下的发射光谱谱图见附图1所示。其最大发射波长在438nm,为深蓝光发光材料。
实施例2:发光材料NOBF2-16的合成
中间体甲氧基醚OCH3-16的合成:在干燥的Schlenk管中加入磁子、中间体1(900mg,3.4mmol,1.0当量)、二苯胺(692mg,4.1mmol,1.2当量)、Pd2(dba)3(62.0mg,0.068mmol,2mol%)、膦配体L1(40mg,0.136mmol,4mol%)、叔丁醇钠(654mg,6.8mmol,2.0当量)。然后排换氮气三次,注射加入甲苯(1mL)和二氧六环(1mL),而后在95℃下反应27小时。薄层色谱监测至原料反应完毕,冷却至室温。减压蒸馏除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:油醚:乙酸乙酯=10:1-5:1,得到黄色黏稠液体588mg,收率49%。1HNMR(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)。
中间体酚OH-16的合成:在25mL单口瓶中加入OCH3-16(588mg,1.67mmol),排换氮气三次后,注射加入二氯甲烷(10mL),逐滴加入BBr3(646μl)。然后在室温下搅拌反应3天,加入少量二氯甲烷稀释,减压除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=10:1-5:1,得到黄色固体437mg,收率为67%。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)。
发光材料NOBF2-16的合成:在25mL单口瓶中加入上述得到的中间体酚OH-16(437mg,1.12mmol,1.0当量),排换氮气三次后,注射加入二氯甲烷(10mL)、三乙胺(3.2mL)和三氟化硼***络合物(2.8mL)。然后在室温下搅拌反应3天,薄层色谱监测至原料反应完毕,冷却至室温。减压除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=5:1-3:1,得到黄绿色固体407mg,收率94%。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)。
发光材料NOBF2-16的甲苯溶液在室温下的发射光谱谱图见附图2所示。其最大发射波长在469nm,为天蓝光发光材料。
实施例3:发光材料NOBF2-18的合成
中间体甲氧基醚OCH3-18的合成:在干燥的Schlenk管中依次加入中间体1(190.2mg,0.72mmol,1.2当量)、二(二联苯基)胺(192.9mg,0.6mmol,1.0当量)、Pd2(dba)3(14.7mg,0.012mmol,2mol%)、膦配体L1(7.2mg,0.024mmol,4mol%)、叔丁醇钠(115.3mg,1.2mmol,2.0当量)。然后排换氮气三次,注射加入甲苯(1mL)和二氧六环(1mL),而后在95℃下反应24小时。薄层色谱监测至原料反应完毕,冷却至室温。减压蒸馏除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=5:1—3:1为洗脱剂,得到浅黄色固体156mg,,收率52%。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)。
中间体酚OH-18的合成:在25mL单口瓶中加入OCH3-18(155mg),乙酸(1mL)和氢溴酸(2mL;浓度48%),然后该混合物在120℃下回流24小时,薄层色谱监测至原料反应完毕,冷却至室温。减压除去溶剂,加入少量水,滴加碳酸钠溶液至不冒泡,过滤干燥得到淡黄色固体87mg,收率60%。直接用于下一步反应。
发光材料NOBF2-18的合成:在25mL单口瓶中加入上述得到的中间体酚OH-18(87mg),排换氮气三次后,注射加入二氯甲烷(8mL)、三乙胺(1.2mL)和三氟化硼***络合物(1.2mL)。然后在室温下搅拌反应3天,薄层色谱监测至原料反应完毕,冷却至室温。减压除去溶剂,粗品用硅胶层析柱进行分离提纯,淋洗剂:石油醚/乙酸乙酯=5:1得到黄色固体25mg,收率25.7%。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)。
发光材料NOBF2-18的甲苯溶液在室温下的发射光谱谱图见附图3所示。其最大发射波长在508nm,为绿光发光材料。
性能评价实施例
以下对本发明上述实施例中所制备的配合物进行光物理分析:
测试条件:室温发射光谱中,所有样品均为甲苯(色谱级)稀溶液(10-5-10-6M)。发光量子效率(PLQY)为发光材料10wt%掺杂的DEPEO薄膜样品测得。其中DEPEO结构如下式所示。
由附图1~4归纳总结此三种发光材料的光物理性质如下表所示。
表1.发光材料的光物理性质
发光材料 | Peak/nm | 量子效率 |
NOBF2-1 | 438(深蓝光) | 80% |
NOBF2-16 | 469(天蓝光) | 75% |
NOBF2-18 | 508(绿光) | 73% |
注:Peak是指发光材料室温下在甲苯溶液中发射光谱的最强发射峰。
从附图1-附图4和表1可知:材料发光颜色极易调控:在保持受体结构不变的情况下,只是通过简单的调节给体的结构即可实现材料的发光颜色由深蓝光至绿光的调控;发光材料的量子效率很高,均在70%以上;且其结构简单,易于合成制备,以上这些性质均有利于其作为掺杂发光体在OLED器件中的应用,并为解决目前急缺的蓝光发光材料提供一个有效的途径,以大大促进此领域的发展。
本领域的普通技术人员可以理解,上述各实施方式是实现本发明的具体实施例,而在实际应用中,可以在形式上和细节上对其作各种改变,而不偏离本发明的精神和范围。例如,在不背离本发明的精神的情况下,这里描述的许多材料和结构可以用其它材料和结构代替。
Claims (6)
1.一类含有二氟化氮-硼-氧杂多环受体结构单元的如式(1)所示的有机发光或热致延迟荧光材料:
其中,
Ra和Rb各自独立地为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、卤素、单或二(C1-C24烷基)氨基、单或二芳基氨基、氰基或其组合;
m和n分别为取代基Ra和Rb的个数,m为0-4的整数,n为0-3的整数;
给体D可以为以下结构之一:
其中,
R1、R2、R10、R11、R12、R13、R14和R15各自独立为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、卤素、单或二(C1-C24烷基)氨基、单或二芳基氨基、氰基或其组合;
其中,o、p、u、v、w、x、y和z分别为取代基R1、R2、R10、R11、R12、R13、R14和R15的个数,o和p各自独立为0-5的整数;u、v、w、x、y和z各自独立为0-4的整数。
2.根据权利要求1所述的有机发光或热致延迟荧光材料,其特征在于:所述的取代基R1、R2、R10、R11、R12、R13、R14和R15各自独立为氢、氘、C1-C24的烷基、C1-C24的烷氧基、C1-C24的环烷基、C1-C24的杂环基、C1-C24的芳基、C1-C24的芳氧基、单或二(C1-C24烷基)氨基、单或二芳基氨基、氰基。
4.一种根据权利要求1至3中任一项所述有机发光或热致延迟荧光材料的应用,为在有机发光器件中作为功能材料使用,所述有机发光器件为有机发光二极管、照明器件。
5.一种有机发光器件,其特征在于,所述有机发光器件包括第一电极、第二电极及以及位于所述阳极和阴极之间的至少一层的有机薄膜,所述有机薄膜中含有权利要求1至3任一项所述的有机发光或热致延迟荧光材料。
6.根据权利要求5所述的有机发光器件,其特征在于,所述含有二氟化氮-硼-氧杂多环受体结构单元的有机发光或热致延迟荧光材料在有机发光器件中作为发光材料、主体材料、或其他功能层材料应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110545959.3A CN113234098B (zh) | 2021-05-19 | 2021-05-19 | 一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110545959.3A CN113234098B (zh) | 2021-05-19 | 2021-05-19 | 一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113234098A CN113234098A (zh) | 2021-08-10 |
CN113234098B true CN113234098B (zh) | 2023-06-13 |
Family
ID=77137550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110545959.3A Active CN113234098B (zh) | 2021-05-19 | 2021-05-19 | 一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113234098B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114560880B (zh) * | 2022-03-02 | 2024-01-26 | 浙江虹舞科技有限公司 | 一类酚氧-吡啶螯合二氟化硼受体构建的有机热激活延迟荧光材料及其应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102040617A (zh) * | 2010-11-24 | 2011-05-04 | 浙江理工大学 | 有机二氟化硼配合物及其制备方法 |
CN102321109A (zh) * | 2011-07-18 | 2012-01-18 | 中国科学院长春应用化学研究所 | 1,3,5,7-四甲基-8-三苯胺基吡咯甲川-二氟化硼络合物及其制备方法 |
CN102993224A (zh) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | 有机二氟化硼配合物 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110759935B (zh) * | 2019-03-12 | 2022-11-01 | 常州大学 | 基于氟硼络合物的蓝色热活性延迟荧光材料及其应用 |
CN110003257B (zh) * | 2019-04-23 | 2021-09-21 | 浙江虹舞科技有限公司 | 一类含有二氟化氮-硼-氧杂环受体结构单元的有机发光材料及其应用 |
-
2021
- 2021-05-19 CN CN202110545959.3A patent/CN113234098B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102040617A (zh) * | 2010-11-24 | 2011-05-04 | 浙江理工大学 | 有机二氟化硼配合物及其制备方法 |
CN102321109A (zh) * | 2011-07-18 | 2012-01-18 | 中国科学院长春应用化学研究所 | 1,3,5,7-四甲基-8-三苯胺基吡咯甲川-二氟化硼络合物及其制备方法 |
CN102993224A (zh) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | 有机二氟化硼配合物 |
Also Published As
Publication number | Publication date |
---|---|
CN113234098A (zh) | 2021-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Pang et al. | Syntheses, structures, and electroluminescence of new blue luminescent star-shaped compounds based on 1, 3, 5-triazine and 1, 3, 5-trisubstituted benzene | |
CN108276449B (zh) | 含有4-芳基-3,5-双取代吡唑的四齿环金属铂配合物、制备方法及应用 | |
CN108948095B (zh) | 基于苯基咔唑的四齿环金属铂配合物及其应用 | |
CN107151312B (zh) | 一种茚并芴基共轭聚合物激光增益材料及制备方法与应用 | |
CN108299507B (zh) | 含有三取代吡唑的四齿环金属铂配合物、制备方法及应用 | |
WO2022223011A1 (zh) | 基于1,8-取代咔唑的高辐射速率铂配合物及应用 | |
CN109575058B (zh) | 4,10-二氧-5,9-二硼芘衍生物、制备方法及应用 | |
CN113234098B (zh) | 一类含有二氟化氮-硼-氧杂环受体的有机发光或热致延迟荧光材料及其应用 | |
CN108659050B (zh) | 含有6-位取代咔唑的四齿环金属铂配合物、制备方法及应用 | |
CN107892704B (zh) | 多齿双核环金属配合物及包含该配合物的器件 | |
CN110003257B (zh) | 一类含有二氟化氮-硼-氧杂环受体结构单元的有机发光材料及其应用 | |
WO2024113800A1 (zh) | 有机发光二极管材料、器件及装置 | |
CN108424425B (zh) | 含有4-芳基-3,5-双取代吡唑的四齿环金属钯配合物、制备方法及应用 | |
CN110183476B (zh) | 双硼氧杂二苯并[a,j]蒽衍生物及其应用 | |
CN109232623B (zh) | 一种硼氮杂菲及其衍生物的合成方法 | |
CN108948096B (zh) | 基于联苯基的四齿环金属铂配合物及其应用 | |
JP2020510986A (ja) | 短い発光減衰時間で単重捕集を直接に得るための有機分子及びその光電子機器における用途 | |
WO2023193596A1 (zh) | 金属铂(ii)和钯(ii)配合物、有机发光器件及显示或照明装置 | |
CN108484676B (zh) | 含有4-芳基-吡唑的四齿环金属铂配合物、制备方法及应用 | |
CN108409794B (zh) | 基于苯基-咔唑的四齿环金属铂配合物及其应用 | |
CN113461545B (zh) | 一种有机磷光组合物及其制备方法和应用 | |
Jiang et al. | Synthesis and characterization of a novel spirocyclic aromatic derivative: unique roles of phenothiazine | |
CN115260249A (zh) | 组合物、制剂、有机电致发光器件及显示或照明装置 | |
CN109678907B (zh) | 一种含有桥连的苯基-苯基-吡唑结构单元的金属铂(ii)配合物 | |
CN109748937B (zh) | 一种含有桥连的苯基-苯基-吡唑结构单元的金属钯(ii)配合物及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |