GB2471584A - Dicarbazole aromatic amine polymers and electronic devices - Google Patents
Dicarbazole aromatic amine polymers and electronic devices Download PDFInfo
- Publication number
- GB2471584A GB2471584A GB1014240A GB201014240A GB2471584A GB 2471584 A GB2471584 A GB 2471584A GB 1014240 A GB1014240 A GB 1014240A GB 201014240 A GB201014240 A GB 201014240A GB 2471584 A GB2471584 A GB 2471584A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymer
- substituted
- group
- aromatic
- toluene
- 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.)
- Granted
Links
- 150000004982 aromatic amines Chemical class 0.000 title abstract description 9
- 229920000642 polymer Polymers 0.000 title description 172
- 125000003118 aryl group Chemical group 0.000 abstract description 62
- 229920000547 conjugated polymer Polymers 0.000 abstract description 24
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 24
- 125000000217 alkyl group Chemical group 0.000 abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 abstract description 21
- 125000005842 heteroatom Chemical group 0.000 abstract description 18
- 125000006574 non-aromatic ring group Chemical group 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 147
- -1 furariyl Chemical group 0.000 description 95
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 239000010410 layer Substances 0.000 description 60
- 229910052757 nitrogen Inorganic materials 0.000 description 51
- 239000000243 solution Substances 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 239000000203 mixture Substances 0.000 description 40
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 27
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000004065 semiconductor Substances 0.000 description 22
- 125000001183 hydrocarbyl group Chemical group 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 20
- 239000012212 insulator Substances 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 19
- 238000010992 reflux Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000004305 biphenyl Substances 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 12
- 239000004020 conductor Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000012043 crude product Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000008096 xylene Substances 0.000 description 11
- PHKYYUQQYARDIU-UHFFFAOYSA-N 3-methyl-9h-carbazole Chemical compound C1=CC=C2C3=CC(C)=CC=C3NC2=C1 PHKYYUQQYARDIU-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 10
- 229920006254 polymer film Polymers 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 150000003738 xylenes Chemical class 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 7
- 230000005669 field effect Effects 0.000 description 7
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical group 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000005693 optoelectronics Effects 0.000 description 5
- WWGXHTXOZKVJDN-UHFFFAOYSA-M sodium;n,n-diethylcarbamodithioate;trihydrate Chemical compound O.O.O.[Na+].CCN(CC)C([S-])=S WWGXHTXOZKVJDN-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- PWJYOTPKLOICJK-UHFFFAOYSA-N 3-methylcarbazole Natural products C1=CC=C2C3=CC=C(C)C=C3NC2=C1 PWJYOTPKLOICJK-UHFFFAOYSA-N 0.000 description 4
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 4
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 4
- 125000000928 benzodioxinyl group Chemical group O1C(=COC2=C1C=CC=C2)* 0.000 description 4
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 4
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 4
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 4
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 4
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 4
- 125000005621 boronate group Chemical group 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000001041 indolyl group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000003384 isochromanyl group Chemical group C1(OCCC2=CC=CC=C12)* 0.000 description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000000615 nonconductor Substances 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 4
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 4
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 4
- 125000005954 phenoxathiinyl group Chemical group 0.000 description 4
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 4
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 125000000168 pyrrolyl group Chemical group 0.000 description 4
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 4
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 4
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 4
- 125000004305 thiazinyl group Chemical group S1NC(=CC=C1)* 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- HMHWNJGOHUYVMD-UHFFFAOYSA-N (4-methylanilino)azanium;chloride Chemical compound Cl.CC1=CC=C(NN)C=C1 HMHWNJGOHUYVMD-UHFFFAOYSA-N 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- KMECXRUKRMYMQU-UHFFFAOYSA-N 3,6-bis(3-methylcarbazol-9-yl)-9-(4-methylphenyl)carbazole Chemical compound C1=CC(C)=CC=C1N1C2=CC=C(N3C4=CC=C(C)C=C4C4=CC=CC=C43)C=C2C2=CC(N3C4=CC=C(C)C=C4C4=CC=CC=C43)=CC=C21 KMECXRUKRMYMQU-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 3
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 2
- VZHJIJZEOCBKRA-UHFFFAOYSA-N 1-chloro-3-fluorobenzene Chemical compound FC1=CC=CC(Cl)=C1 VZHJIJZEOCBKRA-UHFFFAOYSA-N 0.000 description 2
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 2
- ZLCMXHALWTYHOY-UHFFFAOYSA-N 3,6-dibromo-9-(4-methylphenyl)carbazole Chemical compound C1=CC(C)=CC=C1N1C2=CC=C(Br)C=C2C2=CC(Br)=CC=C21 ZLCMXHALWTYHOY-UHFFFAOYSA-N 0.000 description 2
- ZVQPLPSCABMKLZ-UHFFFAOYSA-N 3-methyl-9-[4-[4-(3-methylcarbazol-9-yl)phenyl]phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC(C)=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=C(C)C=C3C3=CC=CC=C32)C=C1 ZVQPLPSCABMKLZ-UHFFFAOYSA-N 0.000 description 2
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- BMBRPEXJJPILQP-UHFFFAOYSA-N 6-methyl-2,3,4,9-tetrahydro-1h-carbazole Chemical compound C1CCCC2=C1NC1=CC=C(C)C=C12 BMBRPEXJJPILQP-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical class CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001543 furan-2,5-diyl group Chemical group O1C(=CC=C1*)* 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002365 multiple layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YSNVKDGEALPJGC-UHFFFAOYSA-N 1,4-difluoro-2-methylbenzene Chemical compound CC1=CC(F)=CC=C1F YSNVKDGEALPJGC-UHFFFAOYSA-N 0.000 description 1
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 1
- AJCSNHQKXUSMMY-UHFFFAOYSA-N 1-chloro-2,4-difluorobenzene Chemical compound FC1=CC=C(Cl)C(F)=C1 AJCSNHQKXUSMMY-UHFFFAOYSA-N 0.000 description 1
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- ZCJAYDKWZAWMPR-UHFFFAOYSA-N 1-chloro-2-fluorobenzene Chemical compound FC1=CC=CC=C1Cl ZCJAYDKWZAWMPR-UHFFFAOYSA-N 0.000 description 1
- FNPVYRJTBXHIPB-UHFFFAOYSA-N 1-chloro-3-fluoro-2-methylbenzene Chemical compound CC1=C(F)C=CC=C1Cl FNPVYRJTBXHIPB-UHFFFAOYSA-N 0.000 description 1
- RJCGZNCCVKIBHO-UHFFFAOYSA-N 1-chloro-4-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1 RJCGZNCCVKIBHO-UHFFFAOYSA-N 0.000 description 1
- BGVGHYOIWIALFF-UHFFFAOYSA-N 1-fluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC=CC=C1C(F)(F)F BGVGHYOIWIALFF-UHFFFAOYSA-N 0.000 description 1
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 description 1
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 1
- IWFKMNAEFPEIOY-UHFFFAOYSA-N 1-fluoro-3,5-dimethoxybenzene Chemical compound COC1=CC(F)=CC(OC)=C1 IWFKMNAEFPEIOY-UHFFFAOYSA-N 0.000 description 1
- GBOWGKOVMBDPJF-UHFFFAOYSA-N 1-fluoro-3-(trifluoromethyl)benzene Chemical compound FC1=CC=CC(C(F)(F)F)=C1 GBOWGKOVMBDPJF-UHFFFAOYSA-N 0.000 description 1
- MFJNOXOAIFNSBX-UHFFFAOYSA-N 1-fluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1 MFJNOXOAIFNSBX-UHFFFAOYSA-N 0.000 description 1
- BTQZKHUEUDPRST-UHFFFAOYSA-N 1-fluoro-3-methylbenzene Chemical compound CC1=CC=CC(F)=C1 BTQZKHUEUDPRST-UHFFFAOYSA-N 0.000 description 1
- UNNNAIWPDLRVRN-UHFFFAOYSA-N 1-fluoro-4-(trifluoromethyl)benzene Chemical compound FC1=CC=C(C(F)(F)F)C=C1 UNNNAIWPDLRVRN-UHFFFAOYSA-N 0.000 description 1
- XZBXPBDJLUJLEU-UHFFFAOYSA-N 1-fluoro-4-methoxy-2-methylbenzene Chemical compound COC1=CC=C(F)C(C)=C1 XZBXPBDJLUJLEU-UHFFFAOYSA-N 0.000 description 1
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- JCHJBEZBHANKGA-UHFFFAOYSA-N 1-methoxy-3,5-dimethylbenzene Chemical compound COC1=CC(C)=CC(C)=C1 JCHJBEZBHANKGA-UHFFFAOYSA-N 0.000 description 1
- KWSHGRJUSUJPQD-UHFFFAOYSA-N 1-phenyl-4-propan-2-ylbenzene Chemical group C1=CC(C(C)C)=CC=C1C1=CC=CC=C1 KWSHGRJUSUJPQD-UHFFFAOYSA-N 0.000 description 1
- OGBJRXBOEMNHLO-UHFFFAOYSA-N 10-(4-butylphenyl)-3,7-bis(3-methylcarbazol-9-yl)phenoxazine Chemical compound C1=CC(CCCC)=CC=C1N1C2=CC=C(N3C4=CC=C(C)C=C4C4=CC=CC=C43)C=C2OC2=CC(N3C4=CC=C(C)C=C4C4=CC=CC=C43)=CC=C21 OGBJRXBOEMNHLO-UHFFFAOYSA-N 0.000 description 1
- UJCFZCTTZWHRNL-UHFFFAOYSA-N 2,4-Dimethylanisole Chemical compound COC1=CC=C(C)C=C1C UJCFZCTTZWHRNL-UHFFFAOYSA-N 0.000 description 1
- WSNLVLNJKOLJKZ-UHFFFAOYSA-N 2,7-dibromo-9,9-bis(4-hexoxyphenyl)fluorene Chemical compound C1=CC(OCCCCCC)=CC=C1C1(C=2C=CC(OCCCCCC)=CC=2)C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 WSNLVLNJKOLJKZ-UHFFFAOYSA-N 0.000 description 1
- ZXQLDWWPVKAPTE-UHFFFAOYSA-N 2,7-dibromo-9,9-bis[4-(2-ethoxyethoxy)phenyl]fluorene Chemical compound C1=CC(OCCOCC)=CC=C1C1(C=2C=CC(OCCOCC)=CC=2)C2=CC(Br)=CC=C2C2=CC=C(Br)C=C21 ZXQLDWWPVKAPTE-UHFFFAOYSA-N 0.000 description 1
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical compound FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 description 1
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- GFNZJAUVJCGWLW-UHFFFAOYSA-N 2-methoxy-1,3-dimethylbenzene Chemical compound COC1=C(C)C=CC=C1C GFNZJAUVJCGWLW-UHFFFAOYSA-N 0.000 description 1
- SJZAUIVYZWPNAS-UHFFFAOYSA-N 2-methoxy-1,4-dimethylbenzene Chemical compound COC1=CC(C)=CC=C1C SJZAUIVYZWPNAS-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- YIUXVMNZXOLRHV-UHFFFAOYSA-N 3,7-dibromo-10-(4-butylphenyl)phenoxazine Chemical compound C1=CC(CCCC)=CC=C1N1C2=CC=C(Br)C=C2OC2=CC(Br)=CC=C21 YIUXVMNZXOLRHV-UHFFFAOYSA-N 0.000 description 1
- QRWWTQHGHBOMPM-UHFFFAOYSA-N 3-bromo-6-methyl-9-phenylcarbazole Chemical compound C12=CC=C(Br)C=C2C2=CC(C)=CC=C2N1C1=CC=CC=C1 QRWWTQHGHBOMPM-UHFFFAOYSA-N 0.000 description 1
- JZTPKAROPNTQQV-UHFFFAOYSA-N 3-fluorobenzonitrile Chemical compound FC1=CC=CC(C#N)=C1 JZTPKAROPNTQQV-UHFFFAOYSA-N 0.000 description 1
- RPHFTDJMHACDKH-UHFFFAOYSA-N 3-methyl-2,3,4,9-tetrahydro-1h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1CCC(C)C2 RPHFTDJMHACDKH-UHFFFAOYSA-N 0.000 description 1
- PXEOGWNOWAUDEI-UHFFFAOYSA-N 3-methyl-9-[4-(3-methylcarbazol-9-yl)phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC(C)=CC=C2N1C1=CC=C(N2C3=CC=C(C)C=C3C3=CC=CC=C32)C=C1 PXEOGWNOWAUDEI-UHFFFAOYSA-N 0.000 description 1
- DAGKHJDZYJFWSO-UHFFFAOYSA-N 4-fluoro-1,2-dimethoxybenzene Chemical compound COC1=CC=C(F)C=C1OC DAGKHJDZYJFWSO-UHFFFAOYSA-N 0.000 description 1
- 229940077398 4-methyl anisole Drugs 0.000 description 1
- 0 CC1=**=C(CCc(cc2)ccc2C(*2O)=**=C2c2ccc(C)cc2)*1* Chemical compound CC1=**=C(CCc(cc2)ccc2C(*2O)=**=C2c2ccc(C)cc2)*1* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NUIMSNCBISYCIM-UHFFFAOYSA-N Cc(cc12)ccc1-c1ccc(C)cc1C2(O)O Chemical compound Cc(cc12)ccc1-c1ccc(C)cc1C2(O)O NUIMSNCBISYCIM-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical group 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 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
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- PLJNHZOEOXGWIR-UHFFFAOYSA-N piroheptine hydrochloride Chemical compound Cl.CC1N(CC)CCC1=C1C2=CC=CC=C2CCC2=CC=CC=C21 PLJNHZOEOXGWIR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/522—Luminescence fluorescent
- C08G2261/5222—Luminescence fluorescent electrofluorescent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A conjugated or partially conjugated polymer comprising a structural unit of Formula I:Wherein Art is an aromatic group which contains one or more heteroatoms, or an aromatic group which comprises one or more fused aromatic or non-aromatic rings, the aromatic group may be substituted or unsubstituted; and R1is alkyl, alkoxy, an aryl group, cyano, or F. An example of the conjugated or partially conjugated polymer is a dicarbazole aromatic amine. Also disclosed are electronic devices comprising the conjugated or partially conjugated polymer.
Description
DESCRI PT ION
DICARBAZOLE AROMATIC AMINE POLYMERS AND
ELECTRONIC DEVICES
This application claims the benefit of the provisional application, U.S. Application No. 60/661,419, filed March 4, 2005, which is incorporated herein by reference.
This invention relates to polymeric compositions comprising N, N'-dicarbazole-based aromatic amine moieties and electronic devices comprising such compositions.
BACKGROUND
Fluorene based conjugated polymers are known to have optoelectronic properties. Several reports have demonstrated blue light emission from fluorene homopolymers e.g., A.W. Grice; D.D.C. Bradley, M.T.
Bernius; M. Inbasekaran, W. Wu, E.P. Woo; Appl. Phys. Lett. 1998, 73, and Y. Young and Q. Pei; J. Appi. Phys. 81, 3294 (1997). By incorporating different aromatic functional groups into the polymer chain, fluorene-based conjugated polymers have demonstrated different emissive colors with the emissive spectra spanning the entire visible range (400 -700 nra) (N. T. Bernius, N. Inbasekaran, J. O'Brien, W. Wu, Adv. Mater. 2000, 12, 1737). Efficient and stable electroluminescence needs efficient injection of holes and electrons into a light-emitting polymer layer from anode and cathode, respectively. Due to the energy mismatch between the highest occupied molecular orbital (HOMO) of fluorene homopolymers and the work function of the anode, the hole-injection of fluorene homopolymers tends to be inefficient. USP 6,309,763, tJSP 6,353,083 and USP 5,879,821 teach the incorporation of triarylamines into fluorene--based polymers as holetransporting moieties to improve the electroluminescent properties of fluorene-based polymers. USPAP 2004127666 further discovered that the inclusion of tricyclic arylamine in the main chain of a fluorene-based optoelectronic polymer provides improved conductivity at low voltages as well as excellent device efficiency compared to polyfluorenes having other charge transporting groups such as acyclic triarylamines (see, tJSP 6,353,083).
A need remains to develop optoelectronic materials and devices that exhibit improved efficiency and lifetime, and emit light in a variety of colors.
Of special interest is to discover new aromatic amine moieties that are suitable to be incorporated into fluorerie-based polymers to offer, for example, deeper blue emission with good hole-injection and hole-transporting properties. N, N' -dicarbazole-based aromatic amines are a well-known class of electronic materials used as hole-injection, hole-transporting, and host materials in small molecule optoelectronic devices. However, N,N'-dicarbazole--based aromatic amines have never been incorporated into the backbone of a conjugated polymer.
SUMMARY OF THE INVENTION
The present invention is directed to a conjugated polymer comprising an N,N'-dicarbazole--based aromatic amine moiety in the main chain of the polymer that exhibits high hole conductivity and deep blue emission.
More specifically, the instant invention is a conjugated or partially conjugated polymer comprising a structural unit of Formula I in the backbone: NAr:Ng wherein Ar1 is an aromatic group which contains one or more heteroatoms, or an aromatic group which comprises one or more fused aromatic or non-aromatic rings, said aromatic group may be substituted or unsubstituted; and R1 is alkyl, alkoxy, an aryl group, cyano, or F. In another embodiment, the invention is a film of a polymer comprising Formula I. In another aspect, the invention is a blend of a polymer comprising Formula I with at least one additional conjugated polymer. In another embodiment, the invention is an electroluminescent device comprising a film comprising a polymer comprising Formula I. In another embodiment, the invention is a photocell comprising a first electrode, a film comprising the polymer comprising Formula I and a second electrode.
JTn another embodiment, the invention is a field effect transistor comprising: (a) an insulator layer, the insulator layer being an electrical insulator, the insulator layer having a first side and a second side; (b) a gate, the gate being an electrical conductor, the gate being positioned adjacent the first side of the insulator layer; Cc) a semiconductor layer, the semiconductor layer comprising the polymer comprising Formula I and a second electrode; (d) a source, the source being an electrical conductor, the source being in electrical contact with the first end of the semiconductor layer; and Ce) a drain, the drain being an electrical conductor, the drain being in electrical contact with the second end of the semiconductor layer.
In another aspect, the invention is a compound of Formula IV R1 () JN-Ari_-N([
U U X R,
V
wherein Ar1 is a substituted or unsubstituted aromatic group which contains one or more heteroatomes or comprises one or more fused aromatic or non-aromatic rings, which rings may be substituted or unsubstituted, R is alkyl, alkoxy, aryl-substituted group, cyano, or F, and X is a halogen or a boronate group.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention is a conjugated or partially conjugated polymer comprising a structural unit of Formula I: wherein Ar1 is an aromatic group which contains one or more heteroatoms, or an aromatic group which comprises one or more fused aromatic or non-aromatic rings, said aromatic group may be substituted or unsubstituted; and R1 is alkyl, alkoxy, an aryl group, cyano, or F. Preferably, Ar1 is selected from the group consisiting of fluorenyl, thiophenyl, furariyl, pyrrolyl, pyridinyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl, perylenyl, quinolinyl, isoquinolinyl, quinazolinyl, phenanthridenyl, phenanthrolinyl, pheriazinyl, acridinyl, dibenzosilolyl, phthalazinyl, cinnolinyl, quinoxalinyl, benzoxazolyl, benzimidazolyl, benzothiophenyl, benzothiazolyl, carbazolyl, benzoxadiazolyl, benzothiadiazolyl, thieno [3,4- b]pyrazinyl, [1,2,5jthiadiazolo[3,4-g]-- quinoxalinyl,benzo[l,2-c;3-4-c'Jbis[l,2,5]-thiadiazolyl, pyrazino [2, 3-g} quinoxalinyl, benzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, thiarithrenyl, benzodioxinyl, benzodioxanyl, dibenzodioxinyl, phenazinyl, phenoxathiinyl, benzodithiinyl, benzodioxolyl, benzocyclobutenyl, dihydrobenzodithiinyl, dihydrothienodioxinyl, chromanyl, isochromanyl, 9,10-dihydrophenanthrenyl, thiazinyl, phenoxazinyl, isoindolyl, dibenzothiophenesulfonyl, and phenothiazinyl, or Ar1 is selected from the group consisting of phenyl, biphenyl, a 9,9-disubstituted- 2,7--f luorenyl, N-substituted--3, 6-carbazolyl, N- substituted-3, 7-phenoxazinyl, N-substituted--3, 7-phenothiazinyl.
In another embodiment, the instant invention is a conjugated or partially conjugated polymer comprising a structural unit of Formula I; wherein Ar1 is biphenyl which may be substituted or unsubstituted, and R1 is alkyl, alkoxy, an aryl group, cyano, or F. In both embodiments, R1 can independently be alkyl, alkoxyl, an aryl group, cyano, or F. Preferably, R1 is a C1-C20 alkyl group, a carbo-C1-C20-alkoxy group, a C1-C20-alkoxy group, which may contain one or more heteroatoms, such as 0, S, N, or Si, and in which one or more hydrogen atoms may be replaced by F, or aromatic groups, or a C6-C40 aryl group which may be further substituted and which may contain one or more heteroatorns. More preferably, R1 is methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl, or tolyl.
In another embodiment, the instant invention is a conjugated or partially conjugated polymer comprising a structural unit of Formula II: N-Ar1-N Ar2] * wherein Ar1 is an aromatic group and Ar2 is another aromatic group which may be the same or different with Ar1, both Ar1 and Ar2 may be substituted or unsubstituted; Ar1 contains one or more heteroatomes or comprises one or more fused aromatic or non-aromatic rings, which rings may be substituted or unsubstituted, and R1 is alkyl, alkoxy, aryl-substituted group, cyano, or F. In another embodiment, the instant invention is a conjugated or partially conjugated polymer comprising a structural unit of Formula II; *
II
wherein Ar1 is biphenyl and Ar2 is another aromatic group which may be the same or different with Ar1, both Ar1 and Ar2 may be substituted or unsubstituted, and R1 is alkyl, alkoxy, an aryl group, cyano, or F. In both embodiments, preferably, Ar2 is a 1,4-phenylene, a 1,3-phenylene, a 1,2-phenylene, a 4,4 -biphenylene, a naphthalene-l, 4-diyl, a naphthalene-2,6-diyl, a furan-2,5-diyl, a thiophene- 2,5-diyl, a 2,2'-bithiophene-5,5-diyl, an anthracene- 9,l0-diyl, a 2,1,3-benzothiadiazole-4,7--diyl, an N-substituted carbazole-3,6--diyl, an N-substituted carbazole'-2, 7-thyl, a dibenzosilole-3, 8-diyl, a dibenzosilole-4, 7-diyl, an N-substituted-phenothiazine- 3, 7-diyl, an N-substituted--phenoxazine-3, 7-diyl, a triarylamirie-diyl including a triphenylamine-4,4'-diyl, a diphenyl-p-tolylamine-4,4'-diyl, and an N,N- diphenylaniline-3,5-diyl, an N,N,N' ,N'-tetraaryl-1,4- diarainobenzene-diyl, an N,N,N' ,N' -tetraarylbenzidine--diyl, an arylsilane-diyl, and an 9,9-disubstituted fluorene-2, 7-diyl.
More preferably, Ar2 comprises a fluorene having the Formula III R2 (R2)n
III
where Q is R' or Ar, wherein Ar is an aryl or heteroaryl group of C4 to C40 or substituted aryl or heteroaryl group of C4 to C40; R' is independently, in each occurrence, H, C.4o hydrocarbyl or C3.4o hydrocarbyl containing one or more S, N, 0, P or Si atoms, or both of R' together with the 9-carbon on the fluorerie may form a C5.2o ring structure that may contain one or more S, N, Si, P or 0 atoms; R2 is independently in each occurrence a C1...40 hydrocarbon, C34o hydrocarbyl containing one or more heteroatoms of 5, N, 0, P or Si, or a substituted or unsubstituted aryl group or heteroaryl group; n is independently in each occurrence, 0-3.
The polymer of the instant invention represented by the formula (I) preferably comprises independently in each occurrence a moiety in the polymer chain selected from the group of conjugated units of the formulas or a combination of the formulas: -ccoc' 0-0
LN to
-01-0-(R3)n NN (R)zi
XI
NC CN
N-N
-o9o-
N
Q
N-N (o)-
-\/ R5 / R5 /
wherein the conjugated units may bear one or more substitutents, such substituents being independently, in each occurrence, C1-2 hydrocarbyl, C1..o hydrocarboxyloxY, C1_20 thioether, C1...20 hydrocarbyloxycarbOnyl, C1...20 hydrocarboxyCarboflYlOxY, cyano, or fluoro group; X1 is 0 or S; Q is R' or Ar; R3 is independently, in each occurrence, C1-20 hydrocarbyl, C1-..20 hydrocarbyloxy, Ci.-20 thioether, C1-20 hydrocarbyloxyCarbOflYl, C2o hydrocarbylcarbOflYlOXY, cyano or fluoro group; R4 is independently, in each occurrence, H, C40 hydrocarbyl or C3..40 hydrocarbyl containing one or more S, N, 0, P or Si atoms, or both of R4 together with the 9-carbon on the fluorene may form a C5.20 ring structure that may contain one or more S, N, Si, P or 0 atoms; and R5 is independently, in each occurrence, H, C,.4o hydrocarbyl or C3..40 hydrocarbyl containing one or more S, N, 0, P or Si atoms; n is independently in each occurrence, 0-3; Ar is an aryl or heteroaryl group of C4 to C40 or substituted aryl or heteroaryl group of C4 to C40; R' is independently, in each occurrence, H, C1..40 hydrocarbyl or C340 hydrocarbyl containing one or more S, N, 0, P or Si. atoms, or both of R' together with the 9-carbon on the fluorene may form a C5..20 ring structure that may contain one or more S, N, Si, P or 0 atoms.
The instant invention includes an electroluminescent device comprising at least one organic film comprising the polymer comprising Formula I, arranged between an anode material and a cathode material such that under an applied voltage, the organic film emits light which is transmitted through a transparent exterior portion of the device.
The instant invention is also a field effect
transistor comprising: (a) an insulator layer, the insulator layer being an electrical insulator, the insulator layer having a first side and a second side; (b) a gate, the gate being an electrical conductor, the gate being positioned adjacent the first side of the insulator layer; Cc) a semiconductor layer, the semiconductor layer comprising the polymer comprising Formula I and a second electrode; (d) a source, the source being an electrical conductor, the source being in electrical contact with the first end of the.
semiconductor layer; and (e) a drain, the drain being an electrical conductor, the drain being in electrical contact with the second end of the semiconductor layer.
The instant invention also includes a photocell comprising a first electrode, a film comprising the polymer comprising Formula I and a second electrode.
In another embodiment, the instant invention is a compound of Formula IV R1 }N-Ari-NJ
U U X R1 Iv
wherein Ar1 is a substituted or unsubstituted aromatic group which contains one or more heteroatomes or comprises one or more fused aromatic or non-aromatic rings, which rings may be substituted or unsubstituted,, R1 is alkyl, alkoxy, aryl-substituted group, cyano, or F, and X is a halogen or a boronate group.
Preferably, Ar3. is selected fr9m the group consisiting of fluorenyl, thiophenyl, furanyl, pyrrolyl, pyridinyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl, perylenyl, quinolinyl, isoquinolinyl, quinazolinyl, phenanthridenyl, phenanthrolinyl, phenazinyl, acridinyl, dibenzosilolyl, phthalazinyl, cirinolinyl, quirioxalinyl, benzoxazolyl, benzimidazolyl, berizothiophenyl, benzothiazolyl, carbazolyl, benzoxadiazolyl, benzothiadiazolyl, thieno [3, 4- b]pyrazinyl, [1,2,5)thiadiazolo[3,4-g]-- quinoxalinyl,benzo[l,2-c;3-4-c'bis[1,2,5)-thiadiazolyl, pyrazino (2, 3-g] quinoxalinyl, benzofuranyl, indolyl, dibenzofuranyl, dibenzothiopheriyl, thianthrenyl, benzodioxinyl, benzodioxanyl, dibenzodioxinyl, phenazinyl, phenoxathiinyl, benzodithiinyl, benzodioxolyl, benzocyclobuteiiyl, dihydrobenzodithiinyl, dihydrothienodioxinyl, chromanyl, isochromanyl, 9,10-dihydrophenanthrenyl, thiazinyl, phenoxazinyl, isoindolyl, dibenzothiophenesulfonyl, and phenothiazinyl, or Ar1 is selected from the group consisting of phenyl, biphenyl, a 9,9-disubstituted-- 2, 7-fluoreriyl, N-substituted-3, 6-carbazolyl, N- substituted-3, 7-phenoxazinyl, N-substituted-3,7--phenothiazinyl.
In another embodiment, the instant invention is a compound of Formula IV R cc t N-Ari-NJ
U U X R1 Iv
wherein Ar1 is substituted or unsubstituted biphenyl, R1 is alkyl, alkoxy, an aryl group, cyano, or F, and X is a halogen or a bororiate group.
In both embodiments, preferably, X is bromine.
R1 is independently alkyl, alkoxyl, aryl-substituted group, cyarlo, or F. R1 preferable Ri is a C1-C alkyl group, a cabo-C1-C20-a1koxy group, a C1-C20-alkoxy group, which may contain one or more heteroatoms, such as 0, S, N, E', or Si, and in which one or more hydrogen atoms may be replaced by F, or aromatic groups, or a C6-C40 aryl group which may be further substituted and which may contain one or more heteroatoms. More preferably, R1 is methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl or tolyl.
The polymers of the invention have a weight average molecular weight of about 10,000 Daltons or greater, 20,000 Daltons or greater, or preferably 50,000 Daltons or greater; 1,000,000 Daltons or less, 500,000 Daltons or less, and preferably 400,000 Daltons or less. Molecular weights are determined using gel permeation chromotography using polystyrene as an internal standard.
The polymers demonstrate a polydispersity (Mw/Mn) of 10 or less, 5 or less, 4 or less and preferably 3 or less.
The polymers of this invention may be assembled by any known coupling reaction for making aromatic compounds. Preferably, the Suzuki coupling reaction is used. The Suzuki reaction couples aromatic compounds using a diboronated aromatic moiety and a dihalogenated aromatic moiety. The reaction allows for the creation of long chain, high molecular weight polymers. Additionally, by controlling the sequence of addition, either random or block copolymers may be produced.
Preferably, the Suzuki reaction starts with a diboronated monomer. The Suzuki process is taught in tJ.S. Patent No. 5,777,070, which is expressly incorporated herein by reference.
Toluene or xylenes are the preferred solvents for the Suzuki reaction to prepare the polymers of the instant invention. Sodium carbonate in water is the preferred base, a palladium complex catalyst, such as tetrakis (triphenylphosphine)palladium or dichiorobis (triphenylphosphine)palladium(II) is the preferred catalyst, and a phase transfer catalyst, preferably, a quaternary ammonium salt, is used to speed up the reaction for achieving high molecular weight in a short period of time.
A general synthetic route is outlined in the following scheme to illustrate the synthetic art of a monomer of Formula II of the instant invention.
Starting materials for synthesizing the monomer(s) of Formula II (wherein, Y is a halogen atom, Ar1, R1, and X are defined as above) of the instant invention, are commercially available from many commercial vendors such as Aldrich Chemical Company.
Ri-Q-44HNH2.HY + AcOH R1C (1) or CJ-NHNH2.HY + AcOI (2) or Pd/a (1) (2) (3) R1 C-N Coupling N_Ari_Ng (3) (4) R1 R1 x
O ___
CN-Ari-NliJ DN-Ari--w.1 o q R1 R1 x (4) (5) 3-Substituted-9-I-l-carbazole (3) may be prepared following a literature procedure (A. R. ICatritzky and Z. Wang, Journal of Heterocyclic Chemistry, 25, 671, (1988); J.-K Luo, R. N. Castle, M. L. Lee, Journal of Heterocyclic Chemistry, 26, 1213, (1989); Crosby U. Rogers and B. B. Corson, Journal of the Iinerican Chemical Society, 69, 2910) starting from a para-substituted or unsubstituted phenyihydrazine hydrohalogenide salt and cyclohexanone or a substituted cyclohexanone. For example, p-tolylhydrazine hydrochloride reacts with cyclohexanone in boiling glacial acetic acid to produce 1,2,3,4-tetrahydro--6- methylcarbazole. The dehydrogenation of 1,2,3,4-tetrahydro-6-methylcarbazole catalyzed by palladium on charcoal at elevated temperatures generates 3-methyl-9- H-carbazole as one example of compound (3). 3-methyl- 9-FI-carbazole can also be prepared starting from phenyihydrazine hydrochloride and 4-methyl--cyclohexanone using the similar reactions, in which the intermediate compound (2) is 1,2,3,4-tetrahydro--3- methylcarbazole. A bis (3-substitute-carbazolyl)arornatic compound (4) can be prepared by reacting a compound. (3) with a dihalogenated aromatic compound, for example, l,4-diiodobenzene, 4,4'-diioctobiphenyl, 3, 6-dibromo-9-p-tolylcarbazole, through a C-N coupling reaction. Useful C-N coupling reactions include and are not limited to the Ullmann reaction (US 4,588,666) arid palladium-catalyzed cross coupling reactions (M. S. Driver, J. F. Hartwig, Journal of the American Chemical Society, 118, 7217 (1996); J. P. Wolfe, S. Wagaw, S. L. Buchwald, Journal of the American Chemical Society, 118, 7215 (1996); J. P. Wolfe and S. L. Buchwald, Journal of Organic Chemistry, 61, 1133 (1996); A. S. Guran, R. A. Rennels, S. L..
Buchwald, Angew. Chem. mt. Ed. Engi., 34, 1348 (1995); L Louie, J. F. Hartwig, Tetrahedron Lett.,. 36, 3609 (1995)). A dihalogenated monomer of compound (5) can be prepared by treating a compound (4) with a halogenation reagent, such as N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), bromine. A dihalogeriated monomer of compound (5) may be further converted to a diboronate monomer using a known art (US 6,169,163; W.-L. Yu, J. Pei, Y. Cao, A. J. Fleeger, Chemical Communications, 1837 (1999); T. Tshiyama, H. Murata, N. Hiyaura, Journal of Organic Chemistry, 60, 7508 (1995)).
Another aspect of this invention is related to polymer blends. The blends comprise a polymer containing structural units of Formula I or Formula I blended with at least one other conjugated polymer, preferably a conjugated polymer. As used herein, the term "conjugated polymer" means a polymer with a backbone of overlapping i-i orbitals. Conjugated polymers that may be used in the blends include polyfluorenes, poly(arylenevinylene), polyphenylenes, polyindenofluorenes and polythiophenes, including homopolymers, co-polymers or substituted homopolymers and/or copolymers of any of these conjugated polymers.
Preferably, the polymer blend is composed of at least 1 weight percent of a polymer containing a structural unit of Formula I. The most preferred polymer blends have high photoluminescent arid electroluminescent efficiency. Other additives such as viscosity modifiers, antioxidants and coating improvers may optionally be added. Additionally, blends of two or more low polydispersity polymers of similar compositions but different molecular weight can also be formulated.
Another aspect of this invention is the films formed from the polymers of the invention. Such films can be used in polymeric light emitting diodes,
photovoltaic cells and field effect transistors.
Preferably, such films are used as emitting layers or charge carrier transport layers. The films may also be used as protective coatings for electronic devices and as fluorescent coatings. The thickness of the film or coating is dependent upon the use.
Generally, such thickness can be from 0.005 to 200 microns. When the coating is used as a fluorescent coating, the coating or film thickness is from 50 to 200 microns. When the coatings are used as electronic protective layers, the thickness of the coating can be from 5 to 20 microns. When the coatings are used in a polymeric light-emitting diode, the thickness of the layer formed is 0.005 to 0.2 microns.
The polymers of the invention form good pinhole-free and defect-free films.
The films are readily formed by coating the polymer composition from another embodiment of this invention in which the composition comprises the polymer and at least one organic solvent. Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Additional solvents which can be used include 1,2,4-trimethylbenzene, 1,2,3,4-tetramethyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2, 6-lutidine, 2-f luoro-m--xylene, 3-fluoro-o--- xylerie, 2-chlorobenzotrifluoride, dimethylformamide, 2- chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3- dimethylpyrazirte, 4-fluoroanisole, 3-fluoroanisole, 3- trifluoro-methylariisole, 2-methylanisole, phenetole, 4- methylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2, 6-dimethylanisole, 3-fluorobenzonitrile, 2,5-dimethylanisole, 2, 4-dimethylanisole, benzoriitrile, 3, 5-dimethylanisole, N,N-dimethylariiline, ethyl benzoate, 1-fluoro-3,5-dimethoxybenzene, 1- methylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzotri fluoride, benzotrifluoride, benzotrifluoride, dioxane, trifluoromethoxyberizene, 4- fluorobenzotrifluoride, 3-f luoropyridine, toluene, 2- fluorotoluene, 2-fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluerie, 2, 5-difluorotoluene, 1- chloro-2, 4-difluorobenzene, 2-fluoropyridine, 3- chlorofluorobenzene, 3-chlorofluorobenzene, 1-chioro- 2, 5-difluorobenzene, 4-chlorofluorobenzene, chioroberizene, o-dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylerie, o-xylene or mixture of 0-, rn-, and p-isomers. It is preferable that such solvents have relatively lowpolarity. High boilers and solvent mixtures are better for ink jetting, but xylenes arid toluene are best for spin coating. Preferably, the solution contains from about 0.1 to 5 percent of a polymer comprising a structural unit of Formula I. Films can be prepared by means well known in the art including spin-coating, spray-coating, dip-coating, roll-coating, offset printing, ink jet printing, screen printing, stamp-coating or doctor blading.
In a preferred embodiment, the invention is a composition comprising a polymer or polymer blend of the invention in a solvent. Solvents which can be used include toluene, xylene, a mixture of o, m and p-isomers of xylene, mesitylene, diethylbenzene, ethylbenzene or benzene derivatives of higher substituted level. Preferably, the solution contains from 0.1 to 10 weight percent of the composition. For thin coatings, it is preferred that the composition contains from 0.5 to 5.0 percent by weight of the composition. The composition is applied to the appropriate substrate by the desired method and the solvent is allowed to evaporate. Residual solvent may be removed by vacuum, heat and/or by sweeping with an inert gas such as nitrogen.
The polymers of this invention demonstrate strong electroluminesence in addition to photoluminesence. Thus, another aspect of the invention relates to organic electroluminescent (EL) devices having a film comprising the polymers of this invention. Preferably, the EL devices of this invention emit light when subjected to an applied voltage of 20 volts or less, 10 volts or less and preferably 6 volts or less.
An organic EL device typically consists of an organic film sandwiched between an anode and a cathode.
When a positive bias is applied to the device, holes are injected into the organic film from the anode, and electrons are injected into the organic film from the cathode. The combination of a hole and an electron may give rise to an excitori that may undergo radiative decay to the ground state by liberating a photon.
In practice, the anode is commonly a mixed oxide of tin and indium for its conductivity and transparency. The mixed oxide (ITO) is deposited on a transparent substrate such as glass or plastic so that the light emitted by the organic film may be observed.
The organic film may be the composite of several individual layers each designed for a distinct function. Because holes are injected from the anode, the layer next to the anode should have the functionality of transporting holes. Similarly, the layer next to the cathode should have the functionality of transporting electrons. In many instances, the electron or hole transporting layer may also act as the emitting layer. In some instances, a single layer may perform the combined functions of hole and electron transport and light emission.
The metallic cathode may be deposited either by thermal evaporation or by sputtering. The thickness of the cathode may be from 1 nm to 1000 rim. The preferred metals are calcium, magnesium, indium, aluminum and barium. A thin layer (1-10 nm) of an alkali or alkaline metal halide, e.g., LIF, NaF, CsF or RbF, may be used as a buffering layer between the light emitting polymer and the cathode, calcium, barium, or magnesium. Alloys of these metals may also be used.
Alloys of aluminum containing 1 to 5 percent of lithium and alloys of magnesium containing at least 80 percent of magnesium are preferred.
In another embodiment, the electroluminescent device comprises at least one hole injecting polymer film (PEDOT film, for example) and a light-emitting polymer film comprised of the composition of the invention, arranged between an anode material and a cathode material such that under an applied voltage, holes are injected from the anode material into the light emitting polymer via the hole-injecting polymer film and electrons are injected from the cathode material into the light-emitting polymer film when the device is forward biased, resulting in light emission from the light-emitting layer. In another embodiment, layers of hole-transporting polymers are arranged so that the layer closest to the anode has the lowest oddation potential, with the adjacent layers having progressively higher oxidation potentials. By these methods, electroluminescent devices having relatively high light output per unit voltage may be prepared.
Another embodiment of the invention relates to photocells comprising one or more of the polymers of the invention wherein the polymers are present as single-layer films or as multiple-layer films, whose combined thickness is in the range of 10 rim to 1000 rim, in the range of 25 rim to 500 run, preferably in the range of 50 rim to 300 rim. When two or more polymers are used, they may be deposited separately as distinct layers or deposited as one layer from a solution containing a blend of the desired polymers.
"Photocells" mean a class of optoelectronic devices that can convert incident light energy into electrical energy. examples of photocells are photovoltaic devices, solar cells, photodiodes, and photodetectors. A photocell generally comprises a transparent or semi-transparent first electrode deposited on a transparent substrate. A polymer film is then formed onto the first electrode that is, in turn, coated by a second electrode. Incident light transmitted through the substrate and the first electrode is converted by the polymer film into excitons that can dissociate into electrons and holes under the appropriate circumstances, thus, generating an electric current.
Another embodiment of the invention relates
to metal-insulator-semiconductor field effect
transistors comprising one or more of the polymers of the invention which serve as a semiconducting polymer.
A field effect transistor comprises five elements. The first element is an insulator layer. The insulator layer is an electrical insulator, having a first side and a second side. The second element is a gate. The gate is an electrical conductor. The gate is positioned adjacent the first side of the insulator layer.
The third element is a semiconductor layer.
The semiconductor layer comprises a polymer comprising a structural unit of Formula I above. The semiconductor layer has a first side, a second side, a first end and a second end, the second side of the semiconductor layer being adjacent to the second side of the insulator layer. The polymer is deposited onto an insulator wherein the polymers are present as single-layer films or as multiple-layer films whose combined thickness is in the range of 10 nm to 1000 rim, in the range of 25 nm to 500 run, preferably in the range of 50 rim to 300 rim.
The fourth element of a field effect
transistor is a source. The source is an electrical conductor. The source is in electrical contact with the first end of the semiconductor layer. The fifth element is a drain. The drain is an electrical conductor. The drain is in electrical contact with the second end of the semiconductor layer. A negative voltage bias applied to the gate causes the formation of a hole conduction channel in the semiconductor layer connecting the source to the drain. A positive bias applied to the gate causes the formation of an electron-conducting channel in the semiconductor layer.
As with electroluminiscent devices, the polymer films comprising the semiconductor layer may be formed by solvent-based processing techniques such as spin-coating, roller-coating, dip-coating, spray-coating and doctor-blading and ink jet printing. When two or more polymers are used, they may be deposited separately as distinct layers or deposited as one layer from a solution containing a blend of the desired polymers.
Two electrodes (source and drain) are attached to the semiconducting polymer and a third electrode (gate) onto the opposite surface of the insulator. If the semiconducting polymer is hole transporting (i.e, the majority carriers are positive holes), then applying a negative DC voltage to the gate electrode induces an accumulation of holes near the polymer-insulator interface, creating a conduction channel through which electric current can flow between the source and the drain. The transistor is in the "on" state. Reversing the gate voltage causes a depletion of holes in the accumulation zone and cessation of current. The transistor is in the "off" state.
Examples
The following examples are included for illustrative purpose and do not limit the scope of the claims.
Reaction Scheme: -CJ-NHNH2.HC + AcOH (1) Pd/C (1) (2) Me + (2) Me Me Br Br2 \f Br (3) (4) Synthesis of 1,2,3,4-Tetrabydro-6-IflethYlcarbazOle (Compound 1) Cyclohexanone (49.1 g, 0.5 moles) and glacial acetic acid (180 g) were charged into a 1L 3-neck round bottom flask (RBF). The solution was heated to reflux.
p-Tolylhydrazine hydrochloride (79.3 g, 0.3 moles) was added under reflux during a period of 1 hour. After the addition of p-tolylhydrazine hydrochloride, the reflux was continued for another 3 hours under nitrogen. The heating mantle was removed and the reaction mixture was cooled and then filtered. The solids were washed with water and then with 300 inL of 75% methanol and filtered. The crude product, collected via filtration, was off-white crystals. The crude product was purified by re-crystallization from methanol to give 70 g of colorless needle crystals as the final product. HPLC indicated a purity of essentially 100 wt%.
Synthesis of 3-1lethylcarbazole (Compound 2) 1, 2,3,4-Tetrahydro-6-rnethylcarbazole (Compound 1) (35 g) and 5% palladium charcoal (12 g) in a 1L RBF were heated at 260°C under nitrogen for 1.5 hour. After cooling down to room temperature, TIff was added to dissolve the compounds. The charcoal arid Pd were removed by filtration. Ti-IF was removed and then the crude product was re-crystallized from ethanol twice. 25.9 g of the final product were obtained as white crystals. HPLC indicated a purity of 99.5 wt%.
Synthesis 4,4' -Bis (3-methylcarbazol-9-yl)biphenyl (Compound 3) lOg (55.2 inmol) of 3-methylcarbazole (Compound 2), 7.47 g (18.4 rnmol) of 4,4'-diiodobiphenyl, 7.1 g (110.4 rnmol) of copper, 30.4 g (0.22 mol) of.potassium carbonate, and 1.45 g (5.5 mmol) of 18-crown-6 were dispersed in 270 rnL of o-dichlorobenzene under nitrogen in a 500 xnL 3-neck RBF equipped with condenser and Dean Stark trap. The suspension was degassed with nitrogen for 15 minutes and then heated to reflux under nitrogen. The water generated during the reaction was removed through the Dean Stark trap. After 16 hours, HPLC showed no starting material of 4,4'-diiodobiphenyl. The reflux was continued for another 4 hours before removing the heating mantle. After the reaction was cooled to near room temperature, the reaction mixture was filtered though a basic alumina bed (-2 cm thick) and eluted with toluene. The solvents were removed on a rotary evaporator under reduced pressure to give white solid as the crude product. The product was purified by re-crystallization from toluene to give white crystals.
HPLC indicated a purity of 99.3 wt%. The product was dried in vacuum oven at 55°C for 2 hours. 8.75 g of white crystals were obtained as the final product.
Synthesis of 4,4 -Bis (3-bromo-6--metliylcarbazol-9-yl)biphenyl (Compound 4) To a solution of 3 g (5.85 inmol) of 4,4'-bis(3-methylcarbazol-9-yl)biphenyl (Compound 3) in 500 rnL of dichioromethane was added dropwise 1.97 g (12.28 mmol) of bromine in 50 mL of dichiorometharie at room temperature. After the addition, the reaction was stirred at room temperature for another 1 h. The mixture was filtered and the crude product was collected by filtration as white solids. Two re-crystallizations from toluene produced the final product as white crystals (0.78 g). HPLC showed a purity of 99.1 wt%.
Reaction Scheme: Me � Me (2) (5) NoNg Me Me Br (6) Synthesis of 1,4-Bis (3-methylcarbazol-9-y]jbenzerie (Compound 5) 7.25 g (40. rnmol) of 3-rnethylcarbazole (Compound 2), 4.95 g (15 mmol) of 1,4-diiodobenzene, 6.4 g (0.1 xnmol) of copper, 28 g (0.22 mol) of potassium carbonate, and 1.3 g (5.5 mmol) of 18-crown-6 were dispersed in 250 niL of o-dichlorobenzene under nitrogen in a 500 rnL 3-neck RBF equipped with condenser and Dean Stark trap. After an overnight reaction, HPLC showed no starting material of 1,4-diiodobenzene. The reflux was continued for another 4 hour before removing the heating mantle. After the reaction was cooled to room temperature, the reaction mixture was filtered through a basic alumina bed (-2 cm thick) and eluted with toluene. The solvents were removed on a rotary evaporator under reduced pressure to give white solid as the crude product. The product was purified by re-crystallization from toluene to give white crystals.
HPLC indicated a purity of 99.6 wt%. The product was dried in a vacuum oven at 55°C overnight. 6.01 g of white crystals were obtained as the final product.
Purity was 99.6 wt% by HPLC. The yield was 91.6 mole%.
Synthesis of 1, 4-Bis (3-bromo-6-methylcarbazol-9-yl)berizene (Compound 6) To a solution of 4.5 g (10.3 rnmol) of 1,4-bis (3-methylcarbazol-9--yl)benzene (Compound 5) dissolved in 700 niL of TFIF was added 3.71 g (20.8 rnrnol) of NBS dissolved in 10 niL of DMF at room temperature. The reaction mixture was stirred at room temperature overnight. White solids precipitated.
HPLC showed a complete conversion of the starting material. The reaction mixture wais heated to reflux and became clear. 1% of NBS was added at room temperature and then heated to ref lux. The reaction mixture was heated to reflux and then cooled down to room temperature to recrystallize the product. White needle crystals were obtained. HPLC showed a purity of 99 wt%. Re-crystallization from THF was repeated once and the purity was increased to 99.4 wt%. The yield was 3.0 g.
Reaction Scheme: Q-, + Cu K2C03 o-DCB
A (7) Br Br
-
methylene chioñde (7) (8) B�=Br + / N Cu,K2C03
----o-DCB
A
(3) (2) (9) () NBS QBr Dir (9) (10) Syzthesis of 9--To1y1-9R-carbazo1e (Compound 7) 16.7 g (0.1 raol) of carbazole, 32.7 g (0.15 mol) of 4-iodotoluene, 12.8 g (02 inol) of copper, 34.5 g (0.25 mol) of potassium, carbonate, and 2.8 g (10 rnmol) of 18-crown--6 were dispersed in 500 mL of o-dichiorobeazene under nitrogen in a 1L 3-neck RBF equipped with condenser and Dean Stark trap. The suspension was degassed with nitrogen for 30 minutes and then heated to reflux under nitrogen. In the first several hours of the reaction, there was some water collected in the Dean Stark trap. The water was removed from the Dean Stark trap. After 22 hours, the reaction was cooled to 70°C, the reaction mixture was filtered through a basic alumina bed (-2 cm thick) and eluted with toluerte. The solvents were removed on a rotary evaporator under reduced pressure to give white solids as the crude product. The product was purified by re-crystallization from the mixture of ethanol and toluene. The yield was 15.25 g. The purity was 99.81% by HPLC.
3, 6-Dibromo-9-p-to].yl-9H--carbazole (Compound 8) To a solution of 15..02 g (58.3 trimol) of 9-tolyl-9}I-carbazole (Compound 7) in 170 mL of dichiorornethane in a 500m1 3-neck RBF was added 20.81 g (116.6 mmol) of N-bromosuccinimide in small portions at 0°C (cooled in ice-water bath). After the addition, the reaction mixture was allowed to warm up to room temperature and was stirred at room temperature overnight. The solvent was then removed on a rotary evaporator and the crude product was purified by re-crystallization from a mixture of ethanol and hexaries.
The yield was 18.68 g. The purity was 99.7% by HPLC 3, 6-Bis (3' th'-yl) -9-to1y1-9H-carbazo1e (Compound 9) 7.25 g (40 inmol) of 3-methylcarbazole (Compound 2), 6.23 g (15 inmol) of 3,6-dibromo--9--p-tolyl-9H-carbazole (8), 6.4 g (0.1 mmol) of copper, 28 g (0.22 mol) of potassium carbonate, and 1.3 g (5.5 mrnol) of 18-crown-6 were dispersed in 250 mL of o-dichlorobenzene under nitrogen in a 500 mL 3-neck REF equipped with condenser and Dean Stark trap and the mixture was heated to reflux. After 4.5 days, an additional 1 g of 3-methylcarbazole was added, and the reflux was continued for another one day. The reaction was then cooled to near room temperature and the reaction mixture was passed through a basic alumina bed (-. 1 inch), eluted with 300 mL of 1,2-dichlorobenzene. After the removal of most of the solvent, the product was precipitated in methanol. The brown solids were re-dissolved in a small amount of toluene and purified on a silica gel column eluted with hexane + toluene (7:3 in volume).. 6.2 g of white solids were obtained and HPLC showed a purity of 98.85%. The white solids were re-crystallized from a mixture of toluene and acetonitrile to give 5.7 g of white solids having a purity of 99.1% as determined by HPLC.
3, 6-Bis (3' -bromo-6'-methylcarbazo3.-9' -yl) -9-p-tolyl-9H-carbazole (Compound 3.0) To a solution of 5.5 g (8.73 mmol) of 3,6-Bis (3' -methylcarbazol-9 -yl) -9--p-tolyl--9H--carbazole (Compound 9) dissolved in 200 mL of THF was added 3.26 g (18.31 mxnol) of N-bromosuccinimide (NBS) dissolved in -10 mL of DMF at room temperature. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated to 50 mL on a rotary evaporator and the product was precipitated into methanol (300 ruL). The crude product was collected as white solids by filtration and then was purified by re-crystallization from a mixture of toluene and ethanol to give the final product as white crystals. The yield was 5.6 g. The purity was 99.8% by HELC.
Reaction Scheme: BrU5tTBr cu:o3.
(2) (11) NNg NBS SrNON (11) (12) 3,7-Bis (3' in 9'-yl) -N-(4-n-butyiphenyl) phenoxazine (Compound 11) 7.1 g (15 inmol) of 3,7-dibromo-N-(4-n-butylphenyl)phenoxazine, 8.14 g of 3-methylcarbazole, 7.1 g of copper, 30.4 g of potassium carbonate, 1.45 g of 18-crown-6 were dispersed in 250 ml of 0-dichlorobenzene under nitrogen in a 500 ml of 3-neck RFB equipped with condenser and Dean-Stark trap. The suspension was degassed with flowed nitrogen for 15 mm. and then was heated to reflux for 7 days. The reaction was allowed to cool to -80°C and was filtered through a basic alumina layer (-2 cm) and washed with 300 ml of o-dichlorobenzene. The combined solutions were evaporated to remove solvent. The crude product was purified by flush chromatography on silica gel eluted with the mixture of toluene and hexanes (2:8 v/v) to give 5.83 grams of the final product as white powders at the purity of 99.3% as indicated by HPLC.
3, 7-Bis (3, -bromo-6' -methylcarbazoi.-9' -yl) -N-(4-n-butyiphenyl) phenoxazine (Compound 12) 3.35 g (5 mmol) of 3,7-bis(3'-methylcarbazol- 9 -yl) -N-(4-n--butylphenyl)phenoxazine dissolved in 200 ml of THF was added 1.8 g (10.1 mmol) of NBS dissolved in 10 ml of DMF at 0°C (ice bath). The reaction mixture was stirred at room temperature overnight. The solvent was removed on rotary evaporator. The crude product was purified by re-crystallization from the mixture of toluerie and ethanol to give the final product as white needle crystals. Yield: 2.7 g.
Purity: 99.8% (HPLC).
Preparation of Polymer 1 -Blue Light-emitting Polymer 2, 7-Bis (1,3, 2-dioxaborolan-2---yl) -9, 9- dioctyifluorene (2.439 g, 4.575 mmol), 2,7-dibromo-9,9-bis(4-(2-ethoxyethoxy)phenyl)fluorene (2.665 g, 4.077 mmol), 4,4 -bis (3-bromo-6-methylcarbazol--9-yl)biphenyl (0.305 g, 0.453 inmol), A1iquat 336 phase transfer agent (0.72 g), and trans-dichioro--bis(triphenylphosphine)palladium (II) (4.2 mg) were dissolved in toluene (40 rnL) with stirring in a 250 rnL 3-necked flask at room temperature. The reaction mixure was then heated to ref lux, whereupon sodium carbonate (2 H, 10 InL) was added. The mixture was stirred for about 2.5 hours, then phenylboronic acid was added (0.27 g), followed by toluene (25 mL), and the reaction mixture was stirred and heated overnight, then allowed to cool. The aqueous phase was separated from the reaction mixture and the organic phase was washed with additional water (100 inL), then added to an aqueous solution of sodium diethyldithiocarbamate trihydrate (DDC, 3 g dissolved in 30 mL water) and heated and stirred under nitrogen at 85°C for 4 hours.
The aqueous phase (16 mL) was separated from the polymer solution, and the organic solution was washed with 2 percent v/v aqueous acetic acid (2 x -100 mL), followed by water washings (3 x -100 mL). The organic phase containing the polymer product was passed through a column of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacuo to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated into methanol.
The polymer was dried overnight in vacuo at 60°C. The polymer was re-dissolved in toluene (170 rnL), and then reprecipitated in methanol. The polymer was collected and dried in vacuo as before to yield 3.9 g of white fibers as the final polymer. GPC analysis of the polymer showed a number average molecular weight (Mn) of 109,000, a weight average molecular weight (Mu) of 210,000, and a polydispersity (M/M) of 1.92.
Preparation of Polymer 2 -Blue Light-emitting Polymer (c27c2j,7c2'°° 2, 7-Bis (1,3, 2-dioxaborolan-2--yl) -9, 9- dioctyifluorene (2.678 g, 5.05 mmol), 2,7-dibromo-9,9--bis(4-(2-ethoxyethoxy)phenyl)fluorerie (2.935 g, 4.50 rnmol), 4', 4-bis (3-bromo-6--methylcarbazol--9-yl)benzene (0.297 g, 0.50 mmol), AliquatTM 336 phase transfer agent (0.6 g), and trans-dichloro-bis(triphenylphosphine)palladium (II) (3 ing) were dissolved in toluene (40 mL) with stirring in a 250 raL 3-necked flask at room temperature. The reaction mixure was then heated to reflux, whereupon sodium carbonate (2 M, 13 ml) was added. The mixture was stirred for about 2.5 hours, then phenylboronic acid was added (0.25 g), followed by toluene (40 mL), and the reaction mixture wais stirred and heated overnight, then allowed to cool. An aqueous solution of sodium diethyldithiocarbamate trihydrate (DDC, 3 g dissolved in 30 rnL water) was added and the mixture was heated and stirred under nitrogen at 95°C for 6 hours. The aqueous phase was separated from the.polymer solution, and the solution was washed with 2 percent v/v aqueous acetic acid (3 x -300 mL), followed by water washings (300 mL). The polymer solution was poured into stirred methanol (3L) to precipitate the polymer. The polymer was collected by filtration and dried in vacuum oven at degrees Celsius overnight. The polymer was re-dissolved in 300 niL of toluene and the solution was passed through a column of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacua to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated in methanol. The polymer was dried overnight in vacuo at degrees Celsius. The polymer was re-dissolved in toluene (200 niL), and then re-precipitated in methanol.
Fibers were collected and dried in vacuo as before to yield 3.5 g of polymer as white fibers. GPC analysis of the polymer showed a number average molecular weight (Ms) of 103,867, a weight average molecular weight (Ma) of 303,412, and a polydispersity (M/M) of 2.92.
Preparation of Po1mer 3 -Phosphorescent Light-emitting Polynter C6H6O 13 fr(\ N\ 2,7-Bis(l,3,2-dioxaborolan-2--yl)-9,9- dihexylfJ.uorene (1.927 g, 4.08 inmol), 2,7-dibromo--9,9-di(4-hexyloxyphenyl)fluorene (2.359 g, 3.48 rnmol), 4,4! -bis (3-bromo-6--niethylcarbazol--9-yl)biphenyl (0.271 g, 0.40 rnmol), an iridium complex monomer with the structure shown below (0.116 g, 0.12 rnmol), AliquatTM 336 phase transfer agent (0.9 g), and trans-dichloro-bis(triphenylphosphine)palladium (II.) (3.6 mg) were dissolved toluene (40 rnL) with stirring in a 250 niL 3-necked flask at room temperature. The reaction raixure was then heated to reflux, whereupon sodium carbonate (2 M, 11 mL) was added. The mixture was stirred under nitrogen overnight, then phenylboronic acid was added (0.27 g), followed by toluene (10 mL), and the reaction mixture was stirred at 101 degrees Celsius for 3.5 h, then allowed to cool. An aqueous solution of sodium diethyldithiocarbamate trihydrate (DDC, 3 g dissolved in 30 niL water) was added and the mixture was heated and stirred under nitrogen at 95°C for 3 hours. The aqueous phase was separated from the polymer solution, and the solution was washed with water (5 x -300 rnL).
The polymer solution was poured into stirred methanol (3L) to precipitate the polymer. The polymer was collected by filtration and dried in vacuum oven at 60 degrees Celsius overnight. The polymer was re-dissolved in 300 mL of toluene and the solution was passed through a column of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacuo to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated in methanol. The polymer was dried overnight in vacua at degrees Celsius. The polymer was re-dissolved in toluene (200 niL), and then re-precipitated in methanol.
The polymer was collected and dried in vacuo as before to yield 2.9 g of the polymer as pale yellow fibers.
GPC analysis of the polymer showed a number average molecular weight (Ma) of 103,867, a weight average molecular weight (Mu) of 303,412, and a polydispersity (MIM) of 2.92. N-s
(y7IrçN rcH=3 Br-<(-Br Preparation of Polymer 4 -Blue Light-emitting Polymer 2c;2j,2c2'&'; 2, 7-Bis (1,3,2-dioxaborolan-2--yl)-9, 9- dioctyifluorene (2.1426 g, 4.04 mmol), 2,7-dibromo-9,9-bis(4-(2-ethoxyethOXy)pheflyl)flUorefle (2.3487 g, 3.60 rnmol), 3,6-bis(3'-bromo--6'-methylCarbaZOl-9'-Y1)-9P-tolyl-9H---carbazole (0.3150 g, 0.40 mmol), AliquatTM 336 phase transfer agent (0.6 g), and trans-dichioro-bis (tripheriylphosphine)palladiuru (II) (2.5 mg) were dissolved in toluene (40 rnL) with stirring in a 250 mL 3-necked flask at room temperature. The reaction mnixure was then heated to reflux, whereupon sodium carbonate (? M, 11 mL) was added. The mixture was stirred for about 2.5 hours, then phenylboronic acid was added (0.25 g), followed by toluene (40 rnL), and the reaction mixture wais stirred and heated overnight, then allowed to cool. An aqueous solution of sodium diethyldithiocarbamate trihydrate (DDC, 3 g dissolved in 30 mL water) was added and the mixture was heated and stirred under nitrogen at 95°C for 6 hours. The aqueous phase was separated from the polymer solution, and the solution was washed with 2 percent v/v aqueous acetic acid (3 x -300 mL), followed by water washings (300 mL). The polymer solution was poured into stirred methanol (3L) to precipitate the polymer. The polymer was collected by filtration and dried in vacuum oven at degrees Celsius overnight. The polymer was re-dissolved in 300 niL of toluene and the solution was passed through a column of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacuo to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated in methanol. The polymer was dried overnight in vacua at degrees Celsius. The polymer was re-dissolved in toluene (200 mL), and then re-precipitated in methanol.
Fibers were collected and dried in vacua as before to yield 2.6 g of polymer as white fibers. GPC analysis of the polymer showed a number average molecular weight (Ma) of 234,239, a weight average molecular weight (4) of 705,872, and a polydispersity (M/M) of 3.01.
Preparation of Polymer 5A -Blue Light-emitting Polymer 2, 7-Bis (1,3, 2-dioxaborolan-2-yl) -9,9- dioctyifluorene (1.8562 g, 3.035 inmol), 2,7-dibrorno- 9, 9-bis(4--(2-ethoxyethoxy)phenyl)fluorene (2.0551 g, 3.15 mmol), 3,7-bis(3'--bromo--6'--methylcarbazol-9'-yl)-N-(4-n-butylphenyl) phenoxazine (0.2911 g, 0.35 mmol), Aliquat 336 phase transfer agent (0.6 g), and trans-dichloro-bis(triphenylphosphine)palladium (II) (2.5 mg) were dissolved in toluene (40 mL) with stirring in a 250 mL 3-necked flask at room temperature. The reaction mixure was then heated to reflux, whereupon sodium carbonate (2 M, 11 ntL) was added. The mixture was stirred for about 2.5 hours, then phenylboronic acid was added (0.25 g), followed by toluene (40 mL), and the reaction mixture wais stirred and heated overnight, then allowed to cool. An aqueous solution of sodium diethyldithiocarbaniate trihydrate (DDC, 3 g dissolved in 30 mL water) was added and the mixture was heated and stirred under nitrogen at 95°C for 6 hours.
The aqueous phase was separated from the polymer solution, and the solution was washed with 2 percent v/v aqueous acetic acid (3 x -300 mL), followed by water washings (300 mL). The polymer solution was poured into stirred methanol (3L) to precipitate the polymer. The polymer was collected by filtration and dried in vacuum oven at 60 degrees Celsius overnight.
The polymer was re-dissolved in 300 mL of toluene and the solution was passed through a column of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacuo to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated in methanol. The polymer was dried overnight in vcuo at 60 degrees Celsius. The polymer was re-dissolved in toluerie (200 ruL), and then re-precipitated in methanol. Fibers were collected and dried in vacuo as before to yield 2.5 g of polymer as white fibers. GPC analysis of the polymer showed a number average molecular weight (Ma) of 161,244, a weight average molecular weight (Mu) of 409,100, and a polydispersity (M/M) of 2.54.
Preparation of Polymer 53 -Alternating Copolymer with Fluorene 17c17' 2,7-Bis(1,3,2-dioxaborolan-2-yl)-9, 9- dioctyifluorene (1.4850 g, 2.80 rninol), 3,7-bis(3'-- bromo-6' -methylcarbazol-9'-yl) -N-(4-n--butylphenyl)phenoxazine (2.3285 g, 2.80 mmol), AliquatTM 336 phase transfer agent (0.6 g), arid trans-dichloro--bis (triphenylphosphine)palladium (II) (2.5 mg) were dissolved in toluene (40 mL) with stirring in a 250 mL 3-necked flask at room temperature. The reaction mixure was then heated to ref lux, whereupon sodium carbonate (2 M, 11 rnL) was added. The mixture was stirred for about 1 day, then phenylbororuic acid was added (0.25 g), followed by toluene (40 mL), and the reaction mixture wais stirred and heated overnight, then allowed to cool. An aqueous solution of sodium diethyldithiocarbamate trihydrate (DDC, 3 g dissolved in 30 niL water) was added and the mixture was heated and stirred under nitrogen at 95°C for 6 hours. The aqueous phase was separated from the polymer solution, and the solution was washed with 2 percent v/v aqueous acetic acid (3 x -300 niL), followed by water washings (300 ml). The polymer solution was poured into stirred methanol (3L) to precipitate the polymer. The polymer was collected by filtration and dried in vacuuni oven at degrees Celsius overnight. The polymer was re-dissolved in 300 niL of toluene and the solution was passed through a coluirirt of celite (1"), silica (3"), and alumina (1") and eluted with toluene. The polymer fractions were combined and the solution concentrated in vacua to produce about a 3 percent w/v solution of polymer in toluene. The product was precipitated in methanol. The polymer was dried overnight in vacua at degrees Celsius. The polymer was re-dissolved in toluene (200 mL), and then re-precipitated in methanol.
Fibers were collected and dried in vacua as before to yield 2.2 g of polymer as white fibers. GPC analysis of the polymer showed a number average molecular weight (Me) of 21,072, a weight average molecular weight (Mu) of 55,716, and a polydispersity (M/M) of 2.64.
Following the similar procedure, the following alternating copolymers were made: Po].,mer 6 C8H17C8H17 Mn 125,433; Mw = 315,200; Polydispersity (Mw/Mn) 2.51 Poliixaer 7 = 50,000; Mw 102,000; Polydispersity (Mw/Mn) 2.04 Polymer B 7c8H,7�) Mn = 23,131; Mw = 84,259; Polydispersity (Mw/Mn) 3.64 Polymer 9 C5H17 8 17 Mn = 21,072; Mw = 55,716; Polydispersity (Mw/Mn) = 2.64 Blue Polymer LED Devices on Li/Cal/Al Cathode Polymer 1 (85 rug) was dissolved in xylenes (5 mL) arid filtered through a 0.22 pL syringe filter. An rim film of 1:16 w/w polyethylenedioxythiophene (PEDOT) :polystyrenesulfonic acid (PSS) was deposited on a cleaned indium-tin-oxide (ITO) coated glass substrate and baked at 200°C for 15 minutes. An 80 nm film of the polymer/xylenes solution was spin-coated onto the PEDOT:PSS film and the coated substrate was baked at 130°C under nitrogen for 1 hour. The cathode layers LiF (3 rim), Ca (10 nm), and Al (150 mu) were then vacuum deposited over the polymer film.
Similarly, Polymer 2, Polymer 4, and Polymer were tested using LiF/Ca/Al as the cathode. The typical device data are summarized in the table below.
Polymers Efficiency Voltage Efficiency -Voltage Luminance C1E (Experiment (cd/A) @ (V) @ (cd/A) @ (V) @ (cd/rn2) @ coordinators 400 cd/rn2 400 cd/rn2 1000 cd/rn2 1000 cd/rn2 10 V (x,y)* Polymer 1 1.1 4.1 1.2 --5.1 3248 (0.17, (02053 604) 0.12) Polymer 2 1.0 4.2 1.1 53 2893 (0.17, (02053604) 0.12) Polymer 4 1.8 4.0 1.9 4.8 -4819 -(0.17, (02053604) 0.12) *Med at the brightness of 200 cd/rn2 As we can see from the data in the table, Polymers 1, 2 and 4 all emitted in deep blue color in the devices using Li/Ca/Al as the cathode.
Blue Polymer LZD Devices on Ba Cathode Polymer 1 (85 mg) was dissolved in xylenes (5 rnL) and filtered through a 0.22 i.IL syringe filter. An ma film of 1:16 w/w polyethylenedioxythiophene (PEDOT) :polystyrenesulfonic acid (PSS) was deposited on a cleaned indium-tin-oxide (ITO) coated glass substrate and baked at 200°C for 15 minutes. An 80 mu film of the polymer/xylenes solution was spin-coated onto the PEDOT:PSS film and the coated substrate was baked at 130°C under nitrogen for 1 hour. The cathode metals Ba (5 nm), and Al (150 nra) were then vacuum deposited over the polymer film.
Similarly, Polymer 2, Polymer 4, and Polymer were tested using LiF/Ca/Al as the cathode. The typical device data are summarized in the table below.
Polymers Efficiency Voltage Eificienc -Voltage -Luminance CIE (Experiment (cd/A) @ (V) @ (cd/A) @ (V) @ (cd/rn2) @ coordinators 400 cd/rn2 400 cd/rn2 1000 cd/rn2 1000 cdhn2 10 V (x,y)* Polymer 1 0.3 5.5 0.4 7.9 1004 (0.159 (02053603) 0.08 1) Polymer 2 0.4 5.5 0.4 -7.7 1108 (0.159, (02053603) 0.084) Polymer 4 1.2 4.6 1.2 5.6 3378 (0.164, (02053603) 0.114) Polymer 5A 1.3 7.0 -1.2 8.9 1480 (0.161, (03053690) 0.129) *Measured at the brightness of 200 cd/m As we can see from the data in the table, Polymers 1, 2, 4, and 5 all emitted in deep blue color in the devices using Ba/Al as the cathode.
Blue Polymer LED Device Using a Blend Comprising Polymer 6 as Emissive Layer: 17 mg of Polymer 6 and 68 mg of poly(9,9-dioctyifluorene) were dissolved in 5 ml of xylenes and the solution was filtered through a 0.22 jiL syringe filter. An 80 nra film of 1:16 w/w polyethylene-dioxythiophene (PEDOT) :polystyrenesuj.fonjc acid (PSS) was deposited on a cleaned indium-tin-oxide (ITO) coated glass substrate and baked at 200°C for 15 minutes. An 80 nra film of the polymer/xylenes solution was spin-coated onto the PEDOT:PSS film and the coated substrate was baked at 130°C under nitrogen for 1 hour.
The cathode layers LiF (3°rim), Ca (10 nra), and Al (150 nm) were then vacuum deposited over the polymer film. The resultant device emitted blue light (CIE coordinates x = 0.160; y 0.080) under dc voltage, and produced an average brightness of 400 cd/rn2 at 7.5 volts with an average light efficiency of 0.2 cd/A. At 10 V, the average brightness of the device was 644 cd/rn2.
Conclusion
While this invention has been described as having preferred aspects, the instant invention can be further modified within the spirit and scope of this disclosure. This application is, therefore, intended to cover any variations, uses, or adaptations of the present invention using the general principles disclosed herein. Further, this application is intended to cover such departures from the present
disclosure as come within the known or customary
practice in the art to which this invention pertains and which fall within the limits of the appended claims. -
EMBODIMENTS
Preferred embodiments of the invention include the following.
[1] A conjugated or partially conjugated polymer comprising a structural unit of Formula I:
N-AI-N
wherein Ar1 is an aromatic group which contains one or more heteroatoms, or an aromatic group which comprises one or more fused aromatic or non-aromatic rings, said aromatic group may be substituted or unsubstituted; and R1 is alkyl, alkoxy, an aryl group, cyano, or F. [2] The polymer of [1] wherein Ar1 is selected from the group consisting of fluorenyl, thiophenyl, furanyl, pyrrolyl, pyridinyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl, perylenyl, quinolinyl, isoquinolinyl, quinazolinyl, phenanthridenyl, phenanthrolinyl, phenazinyl, acridinyl, dibenzosilolyl, phthalazinyl, cinnolinyl, quinoxalinyl, benzoxazolyl, benzimidazolyl, benzothiophenyl, benzothiazolyl, carbazolyl, benzoxadiazolyl, benzothiadiazolyl, thieno[3,4- b]pyrazinyl, [1,2,5]thiadiazolo[3,4-g]-quinoxalinyl, benzo[ 1,2-c;3-4-c']bis[ 1,2,5]-thiadiazolyl, pyrazino [2,3 -g]quinoxalinyl, benzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, thianthrenyl, benzodioxinyl, benzodioxanyl, dibenzodioxinyl, phenazinyl, phenoxathiinyl, benzodithiinyl, benzodioxolyl, benzocyclobutenyl, dihydrobenzodiethiinyl, dihydrothienodioxinyl, chromanyl, isochromanyl, 9,10-dihydrophenanthrenyl, thiazinyl, phenoxazinyl, isoindolyl, dibenzothiophenesulfonyl, and phenothiazinyl.
[3] The polymer of [1], wherein Ar1 is selected from the group consisting of phenyl, biphenyl, a 9,9-disubstituted-2,7-fluorenyl, N-substituted-3,6-carbazolyl, N-substituted-3,7-phenoxazinyl, N-substituted-3,7-phenothiazinyl.
[4] A conjugated or partially conjugated polymer comprising a structural unit of Formula I; NAr1J wherein Ar1 is biphenyl which may be substituted or unsubstituted, and R1 is alkyl, alkoxy, an aryl group, cyano, or F. [5] The polymer of [1] or [4], wherein R1 is independently alkyl, alkoxyl, an aryl group, cyano, or F. [6] The polymer of[1] or [4], wherein R1 is a C1-C20 alkyl group, a carbo-C1-C20-alkoxy group, a C1-C20-alkoxy group, which may contain one or more heteroatoms, such as 0, 5, N, or Si, and in which one or more hydrogen atoms may be replaced by F, or aromatic groups, or a C6-C40 aryl group which may be further substituted and which may contain one or more heteroatoms.
[7] The polymer of[l] or [4], wherein R1 is methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl or tolyl.
[8] A conjugated or partially conjugated polymer comprising a structural unit of Formula II: herein Ar1 is an aromatic group and Ar2 is another aromatic group which may be the same or different with Ar1, both Ar1 and Ar2 may be substituted or unsubstituted; Ar1 contains one or more heteroatoms or comprises one or more fused aromatic or non-aromatic rings, which rings may be substituted or unsubstituted, and R1 is alkyl, alkoxy, aryl-substituted group, cyano, or F. [9] A conjugated or partially conjugated polymer comprising a structural unit of Formula II; wherein Ar1 is biphenyl and Ar2 is another aromatic group which may be the same or different with Ar1, both Ar1 and Ar2 maybe substituted or unsubstituted, and R, is alkyl, alkoxy, an aryl group, cyano, or F. [10] The polymer of[8] or [9], wherein Ar2 is a 1,4-phenylene, a 1,3-phenylene, a 1,2-phenylene, a 4,4'-biphenylene, a naphthalene-l,4-diyl, a naphthalene-2,6-diyl, a furan-2, 5-diyl, a thiophene-2,5 -diyl, a 2,2'-bithiophene-2,5 -diyl, an anthracene-9, 1 0-diyl, a 2,1,3-benzothiadiazole-4,7-diyl, an N-substituted carbazole-3,6-diyl, an N-substituted carbazole-2,7-diyl, a dibenzosilole-3,8-diyl, a dibenzosilole-4,7-diyl, an N-substituted-phenothiazine-3,7-diyl, an N-substituted-phenoxazine-3,7-diyl, a triarylamine-diyl including a triphenylamine-4,4'-diyl, a diphenyl-p-tolylamine-4,4'-diyl, and an N,N-diphenylaniline-3, 5-diyl, an N,N,N',N'-tetraaryl-1,4-diaminobenzene-diyl, an N, N, N',N'-tetraarylbenzidine-diyl, an arylsilane-diyl, and an 9,9-disubstituted fluorene-2,7-diyl.
[11] The polymer of [8] or [9], wherein Ar2 comprises a fluorene having the Formula III (R2) where Q is R' or Ar, wherein Ar is an aryl or heteroaryl group of C4 to C40 or substituted aryl or heteroaryl group of C4 to C40; R' is independently, in each occurrence, H, CMO hydrocarbyl or C30 hydrocarbyl containing one or more S, N, 0, P or Si atoms, or both of R' together with the 9-carbon on the fluorene may form a C5 20 ring structure that may contain one or more S, N, Si, P or 0 atoms; R2 is independently in each occurrence a C10 hydrocarbon, C30 hydrocarbyl containing one or more heteroatoms of S, N, 0, P or Si, or a substituted or unsubstituted aryl group or heteroaryl group; n is independently in each occurrence, 0-3.
[12] The polymer of [1] or [4], further comprising independently in each occurrence a moiety in the polymer chain selected from the group of conjugated units of the formulas or a combination of the formulas: -cxco 0-0 \=J 0 c-z -8-ir)
XI (R3)n
3-c�=-çr NN)n xl
NC CN
N-N
-9 -ovo--
Q Q
N-N -t(o, -cci R4 R4 (R3)
R4 R4 (R3) (R3) 10:::::: _/ 0/N0 wherein the conjugated units may bear one or more substituents, such substituents being independently, in each occurrence, C20 hydrocarbyl, C120 hydrocarboxyloxy, C 1-20 thioether, C1 20 hydrocarbyloxycarbonyl, C1 hydrocarboxycarbonlyoxy, cyano, or fluoro group; X1isOorS; Q isR' orAr; R3 is independently, in each occurrence, Cr20 hydrocarbyl, Cr20 hydrocarboxyloxy, C120 thioether, C120 hydrocarbyloxycarbonyl, Cr20 hydrocarboxycarbonlyoxy, cyano, or fluoro group; R4 is independently, in each occurrence, H, C0 hydrocarbyl or C30 hydrocarbyl containing one or more S, N, 0, P or Si atoms, or both of R4 together with the 9-carbon on the fluorene may form a C520 ring structure that may contain one or more 5, N, Si, P or 0 atoms; R5 is independently in each occurrence, H, C40 hydrocarbyl, or C340 hydrocarbyl containing one or more S, N, 0, P or Si atoms, n is independently in each occurrence, 0-3; Ar is an aryl or heteroaryl group of C4 to C40 or substituted aryl or heteroaryl group of C4 to C40; R' is independently, in each occurrence, H, C10 hydrocarbyl or C30 hydrocarbyl containing one or more S, N, 0, P or Si atoms, or both of R' together with the 9-carbon on the fluorene may form a C520 ring structure that may contain one or more 5, N, Si, P or 0 atoms.
[13] The polymer of[l], [4] [8] or [9] further comprising a solvent.
[14] A film comprising the polymer of [1], [4] [8] or [9].
[15] The polymer of[1J, [4] [8] or [9] blended with at least one additional conjugated polymer.
[16] The polymer of[l], [4] [8] or [9] wherein the polymer emits light in the deep blue range of the spectrum.
[17] An electroluminescent device comprising at least one organic film comprising the polymer of[l], [4] [8] or [9], arranged between an anode material and a cathode material such that under an applied voltage, the organic film emits blue light which is transmitted through a transparent exterior portion of the device.
[18] A field effect transistor comprising:
(a) an insulator layer, the insulator layer being an electrical insulator, the insulator layer having a first side and a second side; (b) a gate, the gate being an electrical conductor, the gate being positioned adjacent the first side of the insulator layer; (c) a semiconductor layer, the semiconductor layer comprising the polymer of[1], [4] [8] or [9] and a second electrode; (d) a source, the source being an electrical conductor, the source being in electrical contact with the first end of the semiconductor layer; and (e) a drain, the drain being an electrical conductor, the drain being in electrical contact with the second end of the semiconductor layer.
[19] A photocell comprising a first electrode, a film comprising the polymer of[1], [4] [8] or [9] and a second electrode.
[20] A compound of Formula IV iv R1 wherein Ar1 is a substituted or unsubstituted aromatic group which contains one or more heteroatoms or comprises one or more fused aromatic or non-aromatic rings, which rings may be substituted or unsubstituted, R1 is alkyl, alkoxy, aryl-substituted group, cyano, or F, and X is a halogen or a boronate group.
[21] A compound of Formula IV
R
N -Ar1----N
IIKIII iv R1
wherein Ar is substituted or unsubstituted biphenyl, R1 is alkyl, alkoxy, an aryl group, cyano, or F, and X is a halogen or a boronate group.
[22] The compound of[20] or [21] wherein X is bromine.
[23] The compound of [20], wherein Ar1 is selected from the group consisting of fluorenyl, thiophenyl, furanyl, pyrrolyl, pyridinyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl, perylenyl, quinolinyl, isoquinolinyl, quinazolinyl, phenanthridenyl, phenanthrolinyl, phenazinyl, acridinyl, dibenzosilolyl, phthalazinyl, cinnolinyl, quinoxalinyl, benzoxazolyl, benzimidazolyl, benzothiophenyl, benzothiazolyl, carbazolyl, benzoxadiazolyl, benzothiadiazolyl, thieno[3,4-b]pyrazinyl, [1,2,5]thiadiazolo[3,4-g]-quinoxalinyl, benzo{ 1,2-c;3-4 c']bis[ 1,2,5] -thiadi azolyl, pyrazino [2,3-g] quinoxalinyl, benzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, thianthrenyl, benzodioxinyl, benzodioxanyl, dibenzodioxinyl, phenazinyl, phenoxathiinyl, benzodithiinyl, benzodioxolyl, benzocyclobutenyl, dihydrobenzodiethiinyl, dihydrothienodioxinyl, chromanyl, isochromanyl, 9,1 0-dihydrophenanthrenyl, thiazinyl, phenoxazinyl, i soindolyl, dibenzothiophenesulfonyl, and phenothiazinyl.
[24] The compound of [20], wherein Ar1 is selected from the group consisting of biphenyl, a 9,9-disubstituted-2,7-fluorenyl, N-substituted-3,6-carbazolyl, N-substituted-3,7-phenoxazinyl, N-substituted-3,7-phenothiazinyl.
[25] The compound of[20] or [21], wherein R1 is independently alkyl, alkoxyl, aryl-substituted group, cyano, or F. [26] The compound of[20] or [21] wherein R1 is a C1-C20 alkyl group, a carbo-C1-C20-alkoxy group, a C1-C20-alkoxy group, which may contain one or more heteroatoms, such as 0, S, N, P, or Si, and in which one or more hydrogen atoms may be replaced by F, or aromatic groups, or a C6-C40 aryl group which may be further substituted and which may contain one or more heteroatoms.
[27] The compound of [20] or [21], wherein R1 is methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, phenyl or tolyl.
[28] A conjugated or partially conjugated polymer comprising a structural unit of Formula II: Ar2
I
wherein Ar1 is an aromatic group and Ar2 is a metal complex monomer, both Ar1 and Ar2 may be substituted or unsubstituted, and R1 is alkyl, alkoxy, aryl group, cyano, or F. [29] A phosphorescent light-emitting polymer comprising the structural unit of Formula I: wherein Ar1 is anaromatic group which may be substituted or unsubstituted, and R1 is alkyl, alkoxy, an aryl group, cyano, or F.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66141905P | 2005-03-04 | 2005-03-04 | |
GB0716882A GB2437899B (en) | 2005-03-04 | 2006-03-02 | Dicarbazole aromatic amine polymers and electronic devices |
Publications (3)
Publication Number | Publication Date |
---|---|
GB201014240D0 GB201014240D0 (en) | 2010-10-13 |
GB2471584A true GB2471584A (en) | 2011-01-05 |
GB2471584B GB2471584B (en) | 2011-03-02 |
Family
ID=43304728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1014240A Expired - Fee Related GB2471584B (en) | 2005-03-04 | 2006-03-02 | Dicarbazole aromatic amine polymers and electronic devices |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2471584B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111019098B (en) * | 2019-12-23 | 2023-05-16 | 黑龙江大学 | Triphenylamine benzothiadiazole polymer containing biphenyl structure, and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030218418A9 (en) * | 2000-10-04 | 2003-11-27 | Mitsubishi Chemical Corporation | Organic electroluminescent device |
WO2005056714A1 (en) * | 2003-12-05 | 2005-06-23 | Eastman Kodak Company | Organic electroluminescent devices |
WO2005057678A1 (en) * | 2003-12-05 | 2005-06-23 | Eastman Kodak Company | Organic electroluminescent devices with additive |
-
2006
- 2006-03-02 GB GB1014240A patent/GB2471584B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030218418A9 (en) * | 2000-10-04 | 2003-11-27 | Mitsubishi Chemical Corporation | Organic electroluminescent device |
WO2005056714A1 (en) * | 2003-12-05 | 2005-06-23 | Eastman Kodak Company | Organic electroluminescent devices |
WO2005057678A1 (en) * | 2003-12-05 | 2005-06-23 | Eastman Kodak Company | Organic electroluminescent devices with additive |
Also Published As
Publication number | Publication date |
---|---|
GB2471584B (en) | 2011-03-02 |
GB201014240D0 (en) | 2010-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8034882B2 (en) | Biscarbazol-9-yl-substituted triarylamine-containing polymers and electronic devices | |
JP5361193B2 (en) | Dicarbazole aromatic amine polymer and electronic device | |
JP5522862B2 (en) | Electroluminescent devices containing tricyclic arylamine polymers | |
TWI460202B (en) | Porphyrin polymer compound and light-emitting element using the same | |
EP2202257A1 (en) | Polymer compound and polymer light-emitting device using the same | |
US20120010359A1 (en) | Salicylate substituted conjugated polymers and devices | |
KR20120109532A (en) | Compound and organic electroluminescent element using said compound | |
CN111247126B (en) | Compound, coating composition comprising the same, and organic light emitting device | |
US20120264977A1 (en) | Triarylamine containing polymers and electronic devices | |
GB2471584A (en) | Dicarbazole aromatic amine polymers and electronic devices | |
JP2023050141A (en) | Composition and light emitting element containing the same | |
JP2023050139A (en) | Composition and light-emitting element containing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20200302 |