CN1769269A - Blocked triarylamine and carbazole materials, methods of treatment and applications thereof - Google Patents
Blocked triarylamine and carbazole materials, methods of treatment and applications thereof Download PDFInfo
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- CN1769269A CN1769269A CN 200510030143 CN200510030143A CN1769269A CN 1769269 A CN1769269 A CN 1769269A CN 200510030143 CN200510030143 CN 200510030143 CN 200510030143 A CN200510030143 A CN 200510030143A CN 1769269 A CN1769269 A CN 1769269A
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- 239000000463 material Substances 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 41
- 125000005259 triarylamine group Chemical group 0.000 title claims description 13
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 150000001716 carbazoles Chemical class 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 56
- -1 carbazole compound Chemical class 0.000 claims description 53
- 239000003153 chemical reaction reagent Substances 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 239000012634 fragment Substances 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000003384 small molecules Chemical class 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 6
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 230000021615 conjugation Effects 0.000 claims description 6
- 230000005669 field effect Effects 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 6
- 125000001725 pyrenyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000005493 quinolyl group Chemical group 0.000 claims description 6
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000005402 stannate group Chemical group 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- 150000004982 aromatic amines Chemical group 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000012776 electronic material Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 230000010354 integration Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229940071182 stannate Drugs 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 150000001502 aryl halides Chemical group 0.000 claims 2
- 239000002841 Lewis acid Substances 0.000 claims 1
- 238000006887 Ullmann reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 150000007517 lewis acids Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- 125000005266 diarylamine group Chemical group 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 1
- 230000001052 transient effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 77
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 44
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 22
- 150000001412 amines Chemical group 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000010025 steaming Methods 0.000 description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229960001866 silicon dioxide Drugs 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- 125000002347 octyl 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])[H] 0.000 description 8
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 229940044174 4-phenylenediamine Drugs 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- UDWOGBVGZXTOLR-UHFFFAOYSA-N 4-n-(4-methylphenyl)benzene-1,4-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=C(N)C=C1 UDWOGBVGZXTOLR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- UJPHBDAPVWFPTG-UHFFFAOYSA-N 9-phenylfluoren-9-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1(O)C1=CC=CC=C1 UJPHBDAPVWFPTG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- UTLXNDJBWUGIIF-UHFFFAOYSA-N C1=CC=CC=C1C1(C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 Chemical compound C1=CC=CC=C1C1(C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 UTLXNDJBWUGIIF-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYSCOZNRIIEFAG-UHFFFAOYSA-N n,n-diphenyl-4-(9-phenylfluoren-9-yl)aniline Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)C1(C2=CC=CC=C2C2=CC=CC=C21)C=1C=CC=CC=1)C1=CC=CC=C1 KYSCOZNRIIEFAG-UHFFFAOYSA-N 0.000 description 1
- WFSRPGWTOHSTEZ-UHFFFAOYSA-N n,n-dithiophen-2-ylthiophen-2-amine Chemical compound C1=CSC(N(C=2SC=CC=2)C=2SC=CC=2)=C1 WFSRPGWTOHSTEZ-UHFFFAOYSA-N 0.000 description 1
- TUJISNOOGRKQOP-UHFFFAOYSA-N n-(4-methylphenyl)-n-thiophen-2-ylthiophen-2-amine Chemical compound C1=CC(C)=CC=C1N(C=1SC=CC=1)C1=CC=CS1 TUJISNOOGRKQOP-UHFFFAOYSA-N 0.000 description 1
- HDLJTTBUZXCRHT-UHFFFAOYSA-N n-phenyl-4-(9-phenylfluoren-9-yl)-n-[4-(9-phenylfluoren-9-yl)phenyl]aniline Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)C1(C2=CC=CC=C2C2=CC=CC=C21)C=1C=CC=CC=1)C1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C=C1 HDLJTTBUZXCRHT-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
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Abstract
The invention, belonging to photoelectric material scientific and technical sphere, relates the new handling method of diarylamine and carbazoles materials and the application as the hole transmission material. Compared with the untreated material, the dead-end diarylamine and carbazoles poessess the high heat stability and glass transition temperature. Comprared with the other methods of preparing the material, the handling method has the following advantages: 1. convenient handling method, simple technology; 2. mild reaction condition, not needing transient metal accelerant; 3. high productivity, direct processing polymeric material; 4. mass production. The said hole transmission material will become the photoelectric material of low cost and commercialization potentiality.
Description
Technical field
The invention belongs to the photoelectric material technical field.Be specifically related to end capped triarylamine and carbazoles material and simple termination process method thereof, and relate to of the application of such material in fields such as organic electroluminescent, organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser.
Technical background
From Tang research group of Kodak [Tang, C.W. in 1987; Van Slyke, S.A.Appl. Phys.Lett.1987,51,913.] and nineteen ninety univ cambridge uk [Burroughes, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Bum, P.L.; Holmes, A.B.Nature 1990,347,539.] delivered respectively make film-type organic electroluminescence device (Organic Light-emittingDiodes) and polymer LED (Polymeric Light-emitting Diodes) with organic and polymer fluorescent material since, organic flat pannel display becomes the demonstration product of the another generation marketization after liquid-crystal display.Meanwhile other organic electronics and photoelectronic industry comprise that field such as organic field-effect tube, organic solar batteries, nonlinear optics, bio-sensing and laser and nonlinear optical material are also just moving towards the marketization.Organic and the advantage plastic electronic product is that the material preparation cost is low, technology simple, has the snappiness and the plasticity-of commodity polymer.Therefore, develop the novel organic photoelectric information material of market potential and attracted the scientist of the different subjects of many domestic and international universities and the concern and the input of research institution and company with practicality.Up to the present, high stability carrier transmission material of development of new and luminescent material become and improve organic electronic, electric light and photoelectric device efficient and life-span key factor.
Up to the present, the organic photoelectrical material that contains 9-aryl-fluorenyl also has high thermostability and high second-order transition temperature when showing good optical and electrical properties, therefore becomes a class practical organic optoelectronic material likely.Therefore, a large amount of articles and patent [Tsukada, Hidetaka have been formed; Totani, Yoshiyuki; Shimamura, Takehiko; Tanabe, Yoshimitsu.Jpn.Kokai Tokkyo Koho (2005), 53pp. patent No. JP2005120030].Yet, this class formation and its derivant structure are carried out the patent that termination process improves the thermostability of organic photoelectrical material as the unit with high second-order transition temperature to material still do not report.Therefore, the present invention has developed a series of end capped triarylamines and carbazoles material by simple termination process method, has introduced simultaneously to have to increase solubleness, the gathering of obstruct chromophoric group or increase stable structural chain to enlarge such material in organic electronic, photoelectron or photoelectric material use range.
Summary of the invention
The objective of the invention is to prepare the amorphous hole mobile material and the derivant material thereof of high stable by the termination process method.In addition, pointed out of the application of such material in organic electronic fields such as organic electroluminescent, organic field-effect tube and laser.
The class that the present invention proposes is through the triarylamine and the carbazoles material of termination process, for containing the material of following structure fragment I:
Symbol in the formula and label have following implication:
-
*Be the position that is connected between triarylamine and carbazoles fertile material and the closed-end structure;
R
1, R
2, R
3, R
4, R
5, Rc
6, R
7, R
8Identical or different during appearance, and be hydrogen; Halogen; Perhaps for to have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or to have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-or SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Perhaps for having alkenylene chain, alkynyl chain or the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and be hydrogen, perhaps for having straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom, perhaps for having the structure of hindered amine chain and oxyalkyl chain;
Ar
1, Ar
2Identical or different during appearance, and for having the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be spiral shell intra-annular Ar
1, Ar
2And the possible position that connects between the carbon of spiral shell center;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
EG
1, EG
2, Ar
3Identical or different during appearance, and, comprise hydrogen, halogen, cyano group and conjugation group for forming the group of single chemical bond; Conjugation unit structure unit wherein has thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, and wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Be specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be EG between the structural unit
1, EG
2With Ar
1, Ar
2The band of position that connects or be Ar
3Link position with spiro atom; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
Ar
4Identical or different during appearance, and be phenyl, thienyl, 3,4-ethyl dioxy thiophene.
Identical or different when n occurs, and independently be 0,1,2,3,4,5,6,7,8,9 or 10;
Contain in the materials process of closed-end structure fragment I in preparation, triarylamine and carbazoles material mainly contain following structure fragment:
Wherein, triarylamine and carbazoles material can be small molecule materials, for example descend array structure:
In the material that contains closed-end structure fragment I, above-mentioned small molecule material can be following structure through after the termination process:
Triarylamine and carbazoles material can be the intermediate feed of preparation hole mobile material, can be following structure as vinylcarbazole and N-alkylhalide group carbazole through termination process:
Contain in the materials process of closed-end structure fragment I in preparation, needed end-capping reagent compound has a kind of in the following structure:
Compound I I
Symbol in the formula and label have following implication:
R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, Ar
1, Ar
2, Ar
3, EG
1, EG
2, same as above when n occurs;
T is hydroxyl or halogen;
In containing structure fragment I compound-material and end-capping reagent, work as Ar
1, Ar
2Identical or different during appearance, and be preferably as follows a kind of in the structure:
In containing structure fragment I compound-material and end-capping reagent, work as EG
1, EG
2Identical or different during appearance, and be preferably as follows a kind of in the structure:
In containing structure fragment I compound-material and end-capping reagent, when containing structure fragment I compound-material and contain one or more structure fragment I, and n is 1, R
1, R
2, R
3, R
4R
5, R
6, R
7, R
8During for hydrogen, Ar
4During for the phenyl structure, contain structure fragment I compound-material and can contain in the following structure any one:
In containing structure fragment I compound-material and end-capping reagent, when n is 1, R
1, R
2, R
3, R
4R
5, R
6, R
7, R
8, EG
1, EG
2During for hydrogen, Ar
4During for the phenyl structure, contain structure fragment I carbazole compound material and be in the following structure any one:
Symbol in the formula and label have following implication:
Ar
1, Ar
2, Ar
3Same as above during appearance;
R
9, R
10, R
11Identical or different during appearance, and for to have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or to have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group;
R
12Identical or different during appearance, and be hydrogen; Halogen; Or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Or having alkenylene chain, alkynyl chain, the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and be hydrogen or straight chain, side chain or the cyclic alkyl chain with 1 to 22 carbon atom or have the structure of hindered amine chain and oxyalkyl chain;
Ar
5Identical person's difference during appearance, and for having the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be Ar between the structural unit
5With R
10The band of position that connects; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-SiR
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
Ar
6Identical or different during appearance, and expression can form the conjugation or the half conjugated structure monomeric repeating unit of double chemical bond, a kind of during its structure is following:
Wherein, symbol in the formula and label have following implication:
-
*Be Ar between the structural unit
6The band of position that is connected with adjacent structure; Greater than two-
*Representative can select arbitrarily wherein two-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-Si R
19R
20-;
E
1, E
2, E
3, E
4Identical or different during appearance, and be CR
19, N or SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement or the oxidized derivatives of its structure.
Identical or different when 1, m occurs, and independence is the numeral between the 1-100;
In containing structure fragment I compound-material and end-capping reagent, when working as R
1～R
12Identical or different during appearance, and when being the hindered amine group chain, have following general formula (VI):
Each symbol implication specific as follows:
-
*Be hindered amine group structural unit and Ar
1, Ar
2, Ar
3, Ar
4, Ar
5, Ar
6The position that can connect;
X, Y are identical or different and are CR
19, or N;
Key between the X-Y is singly-bound or two key;
R
21, R
22, R
23, R
24For identical or different, and be H or straight chain, ring-type or collateralization alkyl and the alkoxyl group with 1 to 22 carbon atom, one or more non-conterminous carbon atom can be by quilt-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement or one or more hydrogen atom can be replaced by fluorine; Perhaps R
21, R
22, R
23, R
24For identical or different, also for having alkylene, aryl and/or the aryloxy of 2 to 40 carbon atoms, one or more carbon atom can be by O, S or N displacement simultaneously; Perhaps the hydrogen on the carbon atom can be replaced by one or more halogens, cyano group;
R
25For identical or different, and be R
24Described structure or be oxyradical, hydroxyl, inferior oxygen base;
X, Y in its formula of (VI) structure can and R
24, R
25Connect into ring;
Nitrogen-atoms in its formula of (VI) structure can be electrically charged.
Contain in the structure fragment I compound-material process synthetic, comprise the synthetic and termination process technology of synthetic, the end-capping reagent of fertile material.Wherein fertile material is the triaryl and the carbazole material of all kinds of documents and patent report, comprises synthetic intermediate, small molecule material and polymer materials.Synthetic method mainly comprises Ullmann and palladium is transition metal-catalyzed and preparation method such as grignard reagent catalysis.
Wherein, Ullmann linked reaction method claims copper catalytic amination reaction again, can prepare small molecules and polymkeric substance, its reactant is secondary aryl amine and aryl dihalide, and in the presence of Anhydrous potassium carbonate and catalytic amount copper, representative condition is as at cuprous iodide (I), with 1,2-dichlorobenzene and hexaoxacyclooctadecane-6-6 is as solvent, and temperature of reaction 120-250 ℃ of scope internal reaction time is 1 to 3 day, obtains high-purity fertile material through column chromatography for separation or recrystallization.For the operation of reaction and the possibility of reaction and the scope of application referring to following document: Gauthier, S.; Frechet, J.M.J.Synthesis 1987,383. these corresponding descriptions as specification sheets with reference to introducing the present patent application.
Wherein, the Buchwald-Hartwig reaction method claims palladium transition metal-catalyzed amination reaction again, and its reactant is arylamines and aryl dihalide, can prepare small molecules and polymkeric substance; Under the condition of alkalescence, as: t-BuONa; Under the condition of palladium catalysis and promotor, as typical Pd (OAc)
2And P
tBu
3Down, with toluene or dioxane as solvent.The possibility of Buchwald-Hartwig reaction and the comprehensive description of difficulty and such reaction are referring to following document: 1. Guram, A.S.; Rennels, R.A.; Buchwald, S.J.Angew.Chem., Int.Ed.Engl.1995,34,1346.; 2. Hartwig, J.F.Angew.Chem., Int.Ed.1998,37,2046-2067.; 3. Wolfe, J.P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S.L.Acc.Chem.Res.1998,31,805-818.; 4. Yang, B.H.; Buchwald, S.L.J.Organomet.Chem.1999,576,125-146.These corresponding descriptions as specification sheets with reference to introducing the present patent application.
Contain in the structure fragment I compound-material process synthetic, synthesizing by following synthetic route of preparation end-capping reagent comprises Gilch, Witting, Stille, Sonogashira, Suzuki, Yamamoto, Heck or Rieke transition metal palladium catalysis process; Comprise other ligations simultaneously by being undertaken by heterocycle Cheng Huan.Preferred Suzuki, Stille are prepared as follows method:
Wherein, the reactant of method (1) Suzuki linked reaction is aryl hypoboric acid and/or aryl dihalide and 2 equivalent aryl list halogenide and/or aryl list boric acid, and perhaps blended aromatic halides/boric acid is realized coupling with palladium catalyst; Catalyst consumption is 0.1 to 20mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day;
Method (2) is the Stille linked reaction: reactant is dihalide and/or two stannates and single stannate and/or single halogenide herein, perhaps corresponding single halogenide-single stannate derivatives monomer, linked reaction under alkaline condition and under the condition of palladium catalyst and solvent existence;
Contain in the structure fragment I compound-material process synthetic, material termination process method is to pass through friedel-crafts reaction: reactant is end-capping reagent and triphenylamine or carbazoles fertile material, and catalyzer is that dehydration generates end capped material under the lewis acidic effect usually.Catalysts is lewis acid catalyst normally, as HCl/ Glacial acetic acid, methanesulfonic/tetracol phenixin, trifluoromethayl sulfonic acid/tetracol phenixin, BF
3/ Et
2Conditions such as O/ methylene dichloride.
Oligomer and high polymer material structure, the thermostability of having tested material by thermogravimetric analysis and differential thermal analysis have been characterized by ultimate analysis, infrared spectra (FTIR), nucleus magnetic resonance (NMR), chromaticness online (GCMS), ground substance assistant laser parsing time-of-fight mass spectrometry (MALDI-TOF-MS), gel chromatography (GPC).
The wherein thermogravimetric analysis of end-blocking material and differential thermal analysis test has shown good thermostability.Therefore, the device of such material composition can effectively be eliminated defect problems such as crystallization and pin hole.Wherein in the test of uv-absorbing and fluorescence emission spectrum, find that reflection has the red shift of general 5-30nm, the while quantum yield contrasts corresponding material and is greatly improved, and the part material character is seen accompanying drawing.
Such compound-material also can be applied to the organic electronic fields such as organic semiconductor layer, solar-energy photo-voltaic cell, organic laser material and organic non linear optical material in the field effect transistor.Compound-material I is suitable for and makes plastic electronic material, photoelectron material; The device in plastic electronic field or element comprise polymkeric substance and organic light emitting diode device, organic solar batteries, organic laser diode component, organic field-effect tube, OTFT, organic integration circuit, bio-sensing device, nonlinear optical element etc.; Use transport material, interface injecting material, conductive material, the photoelectric material that comprises as luminescent material and hole as organic electronic material.
One or more contain hindered amine group compound-material I and add use on a small quantity as the direct use of active material or as auxiliary agent; As promoter material mainly is the stabiliser materials and the optical brightener of heat, light, oxygen, wherein stabiliser materials can add in above-mentioned all kinds of organic electronics and the photoelectron material and general and engineering polymers material in; Add using amount ranges 0.01%～80% as auxiliary agent, is benchmark with the quality of active material.
In addition, on this basis, the various influences that preliminary device is estimated the end-blocking material have been designed to the behavior of device light emission.Device during at the luminescent properties of the injection of current carrier and transmission performance, material and as white light and phosphorescent light body material Subjective and Objective transmission ofenergy behavior and light amplification behavior design and study.Transparent anode is produced on on glass or the plastic, the triarylamine class hole mobile material of vacuum evaporation termination process of the present invention on conductive layer then, evaporation or spin coating luminescent layer or doped body material, evaporation one deck electron transfer layer, evaporation negative electrode at last again.Compound-material I is as OLED and PLED device material, wherein the structure of electroluminescent device is transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, wherein exist, perhaps as the device of the material of main part of the material of main part of white light and phosphorescence as hole transmission layer or electronic barrier layer.The device property test shows that end capped thiofuran material major advantage of the present invention is:
1. the not end capped material of contrast has high glass transition temperature and high thermal stability.
2. device shows better spectrum stability.
Description of drawings
Fig. 1. the structural characterization of three (4-(9-phenyl-fluorenes-9-yl) benzene) amine.Wherein figure (a) expression
1H spectrogram, (b) expression
13The C spectrogram.
Fig. 2. the hot analysis and characterization of triphenylamine.Wherein Fig. 2 (a) represents the thermogravimetric analysis result; Fig. 2 (b) expression DSC differential calorimetric scanning analysis result.
Fig. 3. the hot analysis and characterization of three (4-(9-phenyl-fluorenes-9-yl) benzene) amine.Wherein Fig. 3 (a) represents the thermogravimetric analysis result; Fig. 3 (b) expression DSC differential calorimetric scanning analysis result.
Embodiment
In order to understand the content of patent of the present invention better, further specify technical scheme of the present invention below by concrete example and legend, specifically comprise the preparation of synthetic, property testing and device.But these embodiments do not limit the present invention.
Embodiment 1,9-phenyl-fluorenes-9-alcohol are handled the end-blocking material preparation of triphenylamine as end-capping reagent:
9-phenyl-fluorenes-9-alcohol
9-phenyl-9H-fluoren-9-ol
(0.502g, 2.1mmol) reaction generates Grignard reagent, and is dissolved in Fluorenone in the 16mL tetrahydrofuran (THF) (2.1mmol) 60 ℃ of reactions 24 hours, generates a large amount of white precipitates, adds saturated colour NHCl at last to get bromo-benzene (2.1mmol) and magnesium Mg
4Ge Shi salt is converted into alcohol.After reaction finishes, extracted with diethyl ether, drying is revolved steaming, sherwood oil: methylene dichloride mixed solvent (3: 2) silicagel column purifying obtains the slightly yellowish solid tertiary alcohol (productive rate is 90%).
GC-MS(EI-m/z)：258.1(M
+).
1H?NMR(400MHz，CDCl
3，ppm)：δ7.691-7.672(d，J＝7.6Hz，2H)，7.406-7.325(m，6H)，7.292-7.236(m，5H)，2.508(s，1H).
13C?NMR(CDCl
3，ppm)：δ150.658，143.391，139.82，129.339，128.698，128.459，127.462，125.633，125.037，120.343，83.85.
N, N-phenylbenzene-4-(9-phenyl-fluorenes-9-yl) aniline
N，N-diphenyl-4-(9-phenyl-fluoren-9-yl)phenylamine
Be dissolved in the methylene dichloride when measuring the pure and mild triphenylamine of 9-phenyl-fluorenes-9-by 1: 1, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains white powder solid N as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization, N-phenylbenzene-4-(9-phenyl-fluorenes-9-yl) aniline (productive rate is 92.5%).
GC-MS(EI-m/z)：485(M
+).
Embodiment 2,9-phenyl-fluorenes-9-alcohol are handled the end-blocking material preparation of triphenylamine as end-capping reagent:
N, N-two (4-(9-phenyl-fluorenes-9-yl) phenyl) aniline
N，N-bis(4-(9-phenyl-fluoren-9-yl)phenyl)phenylamine
Be dissolved in the methylene dichloride when measuring the pure and mild triphenylamine of 9-phenyl-fluorenes-9-by 2: 1, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid N as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization, N-two (4-(9-phenyl-fluorenes-9-yl) phenyl) aniline (productive rate is 91%).
MALDI-TOF-MS(m/z)：725.4(M
+).
Embodiment 3,9-phenyl-fluorenes-9-alcohol are handled the end-blocking material preparation of triphenylamine as end-capping reagent:
Three (4-(9-phenyl-fluorenes-9-yl) benzene) amine
tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine
Be dissolved in the methylene dichloride when measuring the pure and mild triphenylamine of 9-phenyl-fluorenes-9-by 3: 1, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid three (four (9-phenyl-fluorenes-9-yl) benzene) amine (productive rate is 90%) as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS(m/z)：965.3(M
+).
1H?NMR(400MHz，CDCl
3，ppm)：δ7.74-7.721(d，J＝7.6Hz，6H)，7.38-7.361(d，J＝7.6Hz，6H)，7.346-7.308(t，J＝7.6Hz，6H)，7.259-7.219(t，J＝7.6Hz，6H)，7.174(s，15H)，6.995-6.974(d，J＝8.4Hz，6H)，6.841-6.82(d，J＝7.6Hz，6H).
13C?NMR(100MHz，CDCl
3，ppm)：δ151.482，146.145，146.037，140.218，139.937，128.984，128.317，128.229，127.805，127.554，126.706，126.362，123.681，120.257，65.131.
Embodiment 4,9-phenyl-fluorenes-9-alcohol are handled N as end-capping reagent, the end-blocking material preparation of N-two (to toluene)-2-thiophenine:
N-(5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl)-two (to toluene) amine
N-(5-(9-phenyl-fluoren-9-yl)thiophen-2-yl)-di(p-tolyl)amine
Ought measure the pure and mild N of 9-phenyl-fluorenes-9-by 1: 1, N-two (to toluene)-2-thiophenine is dissolved in the methylene dichloride, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid N-(5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl)-two (to toluene) amine (productive rate is 98%) as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization.
GC-MS(EI-m/z)：519(M
+).
Embodiment 5,9-phenyl-fluorenes-9-alcohol are handled N as end-capping reagent, the end-blocking material preparation of N-two (thiophene-2-yl) para-totuidine:
N, N-two (5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl) para-totuidine
N，N-bis(5-(9-phenyl-fluoren-9-yl)thiophen-2-yl)p-tolylamine
N, N-two (thiophene-2-yl) para-totuidine
N，N-bis(thiophen-2-yl)p-tolylamine
Ought measure the pure and mild N of 9-phenyl-fluorenes-9-by 2: 1, N-two (thiophene-2-yl) para-totuidine is dissolved in the methylene dichloride, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride is as the silicagel column purifying of leacheate, obtain pale yellow powder solid N with tetrahydrofuran (THF) and sherwood oil recrystallization, N-two (5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl) para-totuidine (productive rate is 95%).
MALDI-TOF-MS(m/z)：751.4(M
+).
Embodiment 6,9-phenyl-fluorenes-9-alcohol are handled the end-blocking material preparation of three (thiophene-2-yl) amine as end-capping reagent:
Three (thiophene-2-yl) amine
tri(thiophen-2-yl)amine
Three (5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl) amine
tris(5-(9-phenyl-fluoren-9-yl)thiophen-2-yl)amine
Ought measure 9-phenyl-fluorenes-9-pure and mild three (thiophene-2-yl) amine solvent in methylene dichloride by 3: 1, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid three (5-(9-phenyl-fluorenes-9-yl) thiophene-2-yl) amine (productive rate is 97.3%) as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization.
MALDI-TOF-MS(m/z)：983.3(M
+).
N, N '-two ((9-phenyl-fluorenes-9-yl) phenyl)-N, N '-two (p-methylphenyl)-1,4-phenylenediamine
N，N′-bis(4-(9-phenyl-fluoren-9-yl)phenyl)-N，N′-bis(p-tolyl)-1，4-Benzenediamine
Ought measure the pure and mild N of 9-phenyl-fluorenes-9-by 2: 1, N '-two (4-aminomethyl phenyl)-N, N '-hexichol-1, the 4-phenylenediamine is dissolved in the methylene dichloride, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid N as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization, N '-two ((9-phenyl-fluorenes-9-yl) phenyl)-N, N '-two (p-methylphenyl)-1,4-phenylenediamine (productive rate is 89.1%).
MALDI-TOF-MS(m/z)：920.5(M
+).
N, N, N ', N '-four ((9-is to octyl phenyl-fluorenes-9-yl) phenyl)-1,4-phenylenediamine
N，N，N′，N′-tetrakis(4-(9-(4-octylphenyl)-fluoren-9-yl)phenyl)-1，4-Benzenediamine
Ought measure 9-by 4: 1 to the pure and mild N of octyl phenyl-fluorenes-9-, N '-two (4-aminomethyl phenyl)-N, N '-hexichol-1, the 4-phenylenediamine is dissolved in the methylene dichloride, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid N as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization, N, N ', N '-four ((9-is to octyl phenyl-fluorenes-9-yl) phenyl)-1,4-phenylenediamine (productive rate is 90.4%).
MALDI-TOF-MS(m/z)：1821.0(M
+).
N, N '-two (4-aminomethyl phenyl)-N, N '-two ((9-phenyl-fluorenes-9-yl) phenyl)-[1,1 '-biphenyl]-4,4 '-diamines
N，N′-bis(4-methylphenyl)-N，N′-bis(4-(9-phenyl-fluoren-9-yl)phenyl)-[1，1′-Biphenyl]-4，4′-diamine
Ought measure the pure and mild N of 9-phenyl-fluorenes-9-by 2: 1, N '-two (4-aminomethyl phenyl)-N, N '-hexichol-[1,1 '-biphenyl]-4,4 '-diamines is dissolved in the methylene dichloride, under the condition of room temperature, drip several boron trifluorides. etherate reaction 30 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride is as the silicagel column purifying of leacheate, obtain pale yellow powder solid N with tetrahydrofuran (THF) and sherwood oil recrystallization, N '-two (4-aminomethyl phenyl)-N, N '-two ((9-phenyl-fluorenes-9-yl) phenyl)-[1,1 '-biphenyl]-4,4 '-diamines (productive rate is 93.3%).
MALDI-TOF-MS(m/z)：996.5(M
+).
N, N, N ', N '-four ((9-is to octyl phenyl-fluorenes-9-yl) phenyl)-hexichol-[1,1 '-biphenyl]-1, the 4-diamines
N，N，N′，N′-tetrakis(4-(9-(4-octylphenyl)-fluoren-9-yl)phenyl)-[1，1′-Biphenyl]-4，4′-diamine
Ought measure 9-by 4: 1 to the pure and mild N of octyl phenyl-fluorenes-9-, N '-two (4-aminomethyl phenyl)-N, N '-hexichol-[1,1 '-biphenyl]-4,4 '-diamines is dissolved in the methylene dichloride, under the condition of room temperature, dripping several boron trifluorides. etherate reaction 30 minutes adds ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, sherwood oil: the mixed solvent of methylene dichloride obtains pale yellow powder solid N, N as the silicagel column purifying of leacheate with tetrahydrofuran (THF) and sherwood oil recrystallization, N ', N '-four ((9-is to octyl phenyl-fluorenes-9-yl) phenyl)-hexichol-[1,1 '-biphenyl]-1,4-diamines (productive rate is 87.3%).
MALDI-TOF-MS(m/z)：1897.0(M
+).
3,6 end capped poly-(N-vinylcarbazole)
3，6-end-capped?poly(9-vinylcarbazole)
Ought measure pure and mild poly-(N-the vinylcarbazole) (M of 9-phenyl-fluorenes-9-by 260: 1
n=25000, PDI=2) be dissolved in 1, in 2-ethylene dichloride or the trichloromethane, under the condition of room temperature, drip several boron trifluorides. etherate reaction 180 minutes, add ethanol and the shrend reaction of going out, dichloromethane extraction, drying is revolved steaming, and the methyl alcohol extracting obtained white solid end capped poly-(N-vinylcarbazole) in 2 days.
GPC：M
n＝79?100；PDI＝2.8.
Embodiment 12, photoluminescence spectra and quantum yield that 9-phenyl-fluorenes-9-alcohol is handled material as end-capping reagent are measured:
Product is made into the trichloromethane dilute solution of 1 μ M accurately, and removes oxygen by argon cleaning.Adopt Tianjin, island UV-3150 ultraviolet-visual spectrometer and RF-530XPC fluorescence spectrophotometer to carry out absorption spectrum and emission spectrometry.Photoluminescence spectra is to measure under the maximum absorption wavelength of uv-absorbing.The photoluminescence spectra of solid film is that the quartz plate by vacuum evaporation carries out, and thickness is 300nm.The fluorescence quantum efficiency of solution is that 10-dibenzanthracene solution or tonka bean camphor I measure as standard by 1 μ M 9 in pimelinketone.
Embodiment 13,9-phenyl-fluorenes-9-alcohol handled the hot assay determination of material as end-capping reagent:
Thermogravimetric analysis (TGA)) carry out on the DTG-60H of Tianjin, island company (Shimadzu) thermogravimetric analyzer, the heating sweep velocity is that 10 ℃/min and nitrogen flow rate are 20cm
3/ min.Differential scanning calorimetry (DSC) carries out on the DSC-60A of Tianjin, island company (Shimadzu) tester, sample at first is heated to the state of low ten degree of decomposed sample temperature with the speed of 10 ℃/min, then, the beginning temperature is got back in cooling under the liquid nitrogen condition, and the same second time is with the speed heat temperature raising scanning of 10 ℃/min.
The heat decomposition temperature of three (4-(9-phenyl-fluorenes-9-yl) benzene) amine is seen accompanying drawing 3 greater than 500 ℃.
Embodiment 14,9-phenyl-fluorenes-9-alcohol is handled the preparation of material as the electroluminescent device of hole mobile material as end-capping reagent:
A bi-layer devices, with three (4-(9-phenyl-fluorenes-9-yl) benzene) amine as the hole transport transport layer, trimerization spiral shell fluorenes is as luminescent layer, be that device architecture is ITO/ three (4-(9-phenyl-fluorenes-9-yl) benzene) amine (20nm)/trimerization spiral shell fluorenes (100nm)/LiF (5 )/Al,, wherein ITO is the transparency electrode of square resistance 10-20 Ω; Three (4-(9-phenyl-fluorenes-9-yl) benzene) amine and trimerization spirofluorene material adopt the vacuum thermal evaporation technology, and evaporation rate 1-2 /s, film thickness are 10～200nm; Evaporation LiF buffer layer again; At last, AM aluminum metallization negative electrode.
Claims (12)
1, the triarylamine of a class termination process and carbazole compound material is characterized in that containing the material of following structure fragment I:
Symbol in the formula and label have following implication:
-
*Be the position that is connected between triarylamine and carbazoles fertile material and the closed-end structure;
R
1, R
2, R
3, R
4R
5, R
6, R
7, R
8Identical or different during appearance, and be hydrogen; Halogen; Perhaps for to have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or to have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Perhaps for having alkenylene chain, alkynyl chain, the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and be hydrogen or straight chain, side chain or the cyclic alkyl chain with 1 to 22 carbon atom or have the structure of hindered amine chain and oxyalkyl chain;
Ar
1, Ar
2Identical or different during appearance, and for having the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be spiral shell intra-annular Ar
1, Ar
2And the possible position that connects between the carbon of spiral shell center;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-Si R
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
Ar
3, EG
1, EG
2Identical or different during appearance, and, comprise hydrogen, halogen, cyano group and conjugation group for forming the group of single chemical bond; Conjugation unit structure unit wherein has thiazolinyl, alkynyl, the aryl of 2 to 40 carbon atoms, and wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Be specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be EG between the structural unit
1, EG
2With Ar
1, Ar
2The band of position that connects or be Ar
3Link position with spiro atom; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-Si R
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
Ar
4Identical or different during appearance, and be phenyl, thienyl, 3,4-ethyl dioxy thiophene;
Identical or different when n occurs, and independently be 0,1,2,3,4,5,6,7,8,9 or 10.
2, compound-material according to claim 1 is characterized in that the end-capping reagent compound has a kind of in the following structure:
Compound I I
Symbol in the formula and label have following implication:
R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, Ar
1, Ar
2, Ar
3, EG
1, EG
2, same as above when n occurs;
T is hydroxyl or halogen.
3, compound-material according to claim 2 is characterized in that working as Ar in the described material and described end-capping reagent that contains structure fragment I
1, Ar
2Identical or different during appearance, and be selected from a kind of in the following structure:
4, compound-material according to claim 2 is characterized in that describedly containing in structure fragment I compound-material and the described end-capping reagent EG
1, EG
2Identical or different during appearance, and select a kind of in the following structure:
5, compound-material according to claim 1 is characterized in that containing one or more structure fragment I when containing structure fragment I compound-material, and n is 1, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, Ar
4During for the phenyl structure, contain structure fragment I compound-material and contain in the following structure any one:
6, compound-material according to claim 1 is characterized in that working as n is 1, R
1, R
2, R
2, R
4R
5, R
6, R
7, R
8, EG
1, EG
2During for hydrogen, Ar
4During for the phenyl structure, contain structure fragment I carbazole compound material and be in the following structure any one:
Symbol in the formula and label have following implication:
Ar
1, Ar
2, Ar
3Same as above during appearance;
R
9, R
10, R
11Identical or different during appearance, and for to have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or to have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group;
R
12Identical or different during appearance, and be hydrogen; Halogen; Or have straight chain, side chain or the cyclic alkyl chain of 1 to 22 carbon atom or have the structure of hindered amine chain, one or more non-conterminous carbon atom can be by-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement, perhaps one or more hydrogen atom is replaced by fluorine or cyano group; Or having alkenylene chain, alkynyl chain, the aryl chain of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group;
R
19, R
20Identical or different during appearance, and be hydrogen or straight chain, side chain or the cyclic alkyl chain with 1 to 22 carbon atom or have the structure of hindered amine chain and oxyalkyl chain;
Ar
5Identical or different during appearance, and for having the aryl of 2 to 40 carbon atoms, wherein one or more carbon atoms can be by heteroatoms Si, Se, O, S, N, S (O)
2Replace, the hydrogen on one or more carbon atoms can be replaced by fluorine or cyano group; Wherein the aryl structure is specially a kind of in the following structure:
Symbol in the formula and label have following implication:
-
*Be Ar between the structural unit
5With R
10The band of position that connects; Greater than one-
*Representative can select arbitrarily one of them-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-Si R
19R
20-;
E
1, E
2, E
3, E
4, E
5, E
6Identical or different during appearance, and be CR
19, N, SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement, the oxidized derivatives of its structure.
Ar
6Identical or different during appearance, and expression can form the conjugation or the half conjugated structure monomeric repeating unit of double chemical bond, a kind of during its structure is following:
Wherein, symbol in the formula and label have following implication:
-
*Be Ar between the structural unit
6The band of position that is connected with adjacent structure; Greater than two-
*Representative can select arbitrarily wherein two-
*As the connection between it;
D
1, D
2, D
3Identical or different during appearance, and be CR
19R
20, NR
19,-O-,-S-,-Se-,-S (O)
2-or-Si R
19R
20-;
E
1, E
2, E
3, E
4Identical or different during appearance, and be CR
19, N or SiR
19
AC
1, AC
2, AC
3, AC
4Identical or different during appearance, and be phenyl, indenyl, naphthyl, Azulene base, fluorenyl, phenanthryl, anthryl, pyrenyl, naphthalene embedding phenyl, thienyl, pyrryl, furyl, imidazolyl, thiazole, pyridyl, pyrazinyl, indyl, benzofuryl, benzothienyl, benzimidazolyl-, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthrolene base; Or be alkyl, fluorine replacement or the oxidized derivatives of its structure;
L, identical or different when m occurs, and independence is the numeral between the 1-100.
7, compound-material according to claim 1 is characterized in that working as R
1～R
12Identical or different during appearance, and when being the hindered amine group chain, have following general formula (VI):
Each symbol implication specific as follows:
-
*Be hindered amine group structural unit and Ar
1, Ar
2, Ar
3, Ar
4, Ar
5, Ar
6The position that can connect;
X, Y are identical or different and are CR
19, or N;
Key between the X-Y is singly-bound or two key;
R
21, R
22, R
23, R
24For identical or different, and be H or straight chain, ring-type or collateralization alkyl and the alkoxyl group with 1 to 22 carbon atom, one or more non-conterminous carbon atom can be by quilt-NR
19-,-O-,-S-,-CO-O-,-O-CO-O-,-CO-NR
19-,-NR
19-CO-NR
19-,-O-CO-S-,-NR
19-CO-O-,-CS-O-,-CS-NR
19-,-O-CS-O-,-NR
19-CS-NR
20-,-O-CS-S-,-NR
19-CS-O-,-CS-S-,-SiR
19R
20-displacement or one or more hydrogen atom can be replaced by fluorine; Perhaps R
21, R
22, R
23, R
24For identical or different, also for having alkylene, aryl and/or the aryloxy of 2 to 40 carbon atoms, one or more carbon atom can be by O, S or N displacement simultaneously; Perhaps the hydrogen on the carbon atom can be replaced by one or more halogens, cyano group;
R
25For identical or different, and be R
24Described structure or be oxyradical, hydroxyl, inferior oxygen base;
X, Y in its formula of (VI) structure can and R
24, R
25Connect into ring;
Nitrogen-atoms in its formula of (VI) structure can be electrically charged.
8, a kind of synthetic method as the described compound-material of one of claim 1～7, it is characterized in that comprising the synthetic and termination process reaction of synthetic, the end-capping reagent of fertile material, wherein fertile material comprises synthetic intermediate, small molecule material and polymer materials, and synthetic method comprises Ullmann reaction and Buchwald-Hartwig amination process;
Wherein, Ullmann linked reaction method is that the catalytic amination reaction of copper is used to prepare small molecules and polymkeric substance, its reactant is secondary aryl amine and aryl halide, in the presence of Anhydrous potassium carbonate and catalytic amount copper, with 1,2-dichlorobenzene and hexaoxacyclooctadecane-6-6 is as solvent, in the temperature of reaction 120-250 ℃ of scope, reaction times is 1 to 3 day, obtains high-purity fertile material through column chromatography for separation or recrystallization;
Wherein, the Buchwald-Hartwig reaction is the transition metal-catalyzed amination reaction of palladium, and its reactant is arylamines and aryl halide, is used to prepare the small molecules fertile material; In the condition of alkalescence with under the condition of palladium catalysis and promotor, as solvent, in the temperature of reaction 120-180 ℃ of scope, the reaction times is 1 to 3 day, obtains high-purity fertile material with toluene or dioxane.
9, synthetic method according to claim 8 is characterized in that the synthetic method of end-capping reagent comprises Gilch, Witting, Stille, Suzuki, Yamamoto, Sonogashira, Heck or Rieke transition metal palladium catalysis process; Comprise other ligations simultaneously by being undertaken by heterocycle Cheng Huan;
Wherein, the reactant of method (1) Suzuki linked reaction is aryl hypoboric acid and/or aryl dihalide and 2 equivalent aryl list halogenide and/or aryl list boric acid, realizes coupling with palladium catalyst; Catalyst consumption is 0.1 to 20mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day;
Method (2) is the Stille linked reaction: reactant is dihalide and/or two stannates and single stannate and/or single halogenide herein, linked reaction under alkaline condition and under the condition of palladium catalyst and solvent existence.
10, synthetic method according to claim 8, it is characterized in that material termination process method adopts friedel-crafts reaction, reactant is end-capping reagent and triarylamine or carbazoles material fertile material, is Lewis acid at catalyzer, and dehydration generates end capped material under the effect of catalyzer.
11, a kind of purposes as the described compound-material of one of claim 1～7 is characterized in that: be suitable for and make plastic electronic material, photoelectron material; The device in plastic electronic field or element comprise polymkeric substance and organic light emitting diode device, organic solar batteries, organic laser diode component, organic field-effect tube, OTFT, organic integration circuit, bio-sensing device, nonlinear optical element; Use transport material, interface injecting material, the conductive material that comprises as luminescent material and hole as organic electronic material; As OLED and PLED device material, wherein the structure of electroluminescent device is transparent anode/hole injection layer/hole transmission layer/electronic barrier layer/luminescent layer hole blocking layer/electron transfer layer/electron injecting layer/negative electrode, wherein except that anode and negative electrode, exist simultaneously simultaneously or not, mainly as the transport layer in luminescent layer and hole and as the material of the body layer of the material of main part of white light and phosphorescence.
12,, it is characterized in that one or more using method that contain the hindered amine group compound-material comprise as active material directly to use or add use on a small quantity as auxiliary agent according to the purposes of the described compound-material of one of claim 1～7; As promoter material mainly is the stabiliser materials and the optical brightener of heat, light, oxygen, wherein stabiliser materials can add in above-mentioned all kinds of organic electronics and the photoelectron material and general and engineering polymers material in; Add using amount ranges 0.01%～80% as auxiliary agent, is benchmark with the quality of active material.
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| WO2010058859A1 (en) * | 2008-11-20 | 2010-05-27 | 住友化学株式会社 | Amine polymer compound and light-emitting element using same |
| CN101397365B (en) * | 2008-11-05 | 2011-08-03 | 南京邮电大学 | 1,8-carbazole polymer optoelectronic material and its preparation and application method |
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