CN113943290A - Polycyclic aromatic compound and application thereof in electroluminescent device - Google Patents
Polycyclic aromatic compound and application thereof in electroluminescent device Download PDFInfo
- Publication number
- CN113943290A CN113943290A CN202010681028.1A CN202010681028A CN113943290A CN 113943290 A CN113943290 A CN 113943290A CN 202010681028 A CN202010681028 A CN 202010681028A CN 113943290 A CN113943290 A CN 113943290A
- Authority
- CN
- China
- Prior art keywords
- ring
- formula
- group
- unsubstituted
- substituted
- 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.)
- Pending
Links
- -1 Polycyclic aromatic compound Chemical class 0.000 title claims abstract description 135
- 150000001875 compounds Chemical class 0.000 claims abstract description 165
- 239000000463 material Substances 0.000 claims abstract description 44
- 125000005259 triarylamine group Chemical group 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 37
- 125000001424 substituent group Chemical group 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 18
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 12
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 12
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 10
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 10
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 10
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims description 10
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 10
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 10
- 125000002541 furyl group Chemical group 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000005561 phenanthryl group Chemical group 0.000 claims description 10
- 125000001725 pyrenyl group Chemical group 0.000 claims description 10
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 10
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 claims description 10
- 125000001544 thienyl group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 8
- 125000001041 indolyl group Chemical group 0.000 claims description 8
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- 125000004502 1,2,3-oxadiazolyl group Chemical group 0.000 claims description 2
- 125000004511 1,2,3-thiadiazolyl group Chemical group 0.000 claims description 2
- 125000004529 1,2,3-triazinyl group Chemical group N1=NN=C(C=C1)* 0.000 claims description 2
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 claims description 2
- 125000004504 1,2,4-oxadiazolyl group Chemical group 0.000 claims description 2
- 125000004514 1,2,4-thiadiazolyl group Chemical group 0.000 claims description 2
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=NC=C1)* 0.000 claims description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 claims description 2
- 125000004506 1,2,5-oxadiazolyl group Chemical group 0.000 claims description 2
- 125000004517 1,2,5-thiadiazolyl group Chemical group 0.000 claims description 2
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 claims description 2
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 claims description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000005874 benzothiadiazolyl group Chemical group 0.000 claims description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 claims description 2
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 claims description 2
- 125000005990 isobenzothienyl group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 2
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 claims description 2
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 claims description 2
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 claims description 2
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 claims description 2
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 130
- 238000003786 synthesis reaction Methods 0.000 description 130
- 150000001793 charged compounds Chemical class 0.000 description 100
- 238000000921 elemental analysis Methods 0.000 description 100
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 100
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 68
- 239000010410 layer Substances 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 35
- 150000001412 amines Chemical class 0.000 description 30
- SXKVNQHLHKDJJF-UHFFFAOYSA-N 2-bromo-3-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=CC(C(O)=O)=C1Br SXKVNQHLHKDJJF-UHFFFAOYSA-N 0.000 description 26
- BXXLTVBTDZXPTN-UHFFFAOYSA-N methyl 2-iodobenzoate Chemical compound COC(=O)C1=CC=CC=C1I BXXLTVBTDZXPTN-UHFFFAOYSA-N 0.000 description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 18
- 238000010992 reflux Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KCENNKQRTLAONS-UHFFFAOYSA-N 2-bromo-5-tert-butyl-3-methoxycarbonylbenzoic acid Chemical compound CC(C)(C)C1=CC(=C(C(=C1)C(=O)OC)Br)C(=O)O KCENNKQRTLAONS-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 13
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 13
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 13
- 230000005525 hole transport Effects 0.000 description 13
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 13
- 238000011056 performance test Methods 0.000 description 13
- 238000010998 test method Methods 0.000 description 13
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- FCTVQOVDYDWVEP-UHFFFAOYSA-N methyl 3-iodonaphthalene-2-carboxylate Chemical compound C1=CC=C2C=C(I)C(C(=O)OC)=CC2=C1 FCTVQOVDYDWVEP-UHFFFAOYSA-N 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- WQVIVQDHNKQWTM-UHFFFAOYSA-N 1-tert-butyl-4-iodobenzene Chemical compound CC(C)(C)C1=CC=C(I)C=C1 WQVIVQDHNKQWTM-UHFFFAOYSA-N 0.000 description 9
- WHMQTPBEFHEYJI-UHFFFAOYSA-N methyl 3-aminonaphthalene-2-carboxylate Chemical compound C1=CC=C2C=C(N)C(C(=O)OC)=CC2=C1 WHMQTPBEFHEYJI-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000011368 organic material Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 6
- MSFZMZDSTSIPFX-UHFFFAOYSA-N n-phenylpyren-1-amine Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1NC1=CC=CC=C1 MSFZMZDSTSIPFX-UHFFFAOYSA-N 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZREJLKXOVGZOQU-UHFFFAOYSA-N 5-[3,5-bis(trifluoromethyl)phenyl]-2-bromo-3-methoxycarbonylbenzoic acid Chemical compound COC(C(C=C(C=C1C(O)=O)C2=CC(C(F)(F)F)=CC(C(F)(F)F)=C2)=C1Br)=O ZREJLKXOVGZOQU-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XTJJSOHOYCCQGJ-UHFFFAOYSA-N 1-(4-iodophenyl)-3,5-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(C(F)(F)F)=CC(C=2C=CC(I)=CC=2)=C1 XTJJSOHOYCCQGJ-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- MGGUROGTKGUOGP-UHFFFAOYSA-N 4-[3,5-bis(trifluoromethyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 MGGUROGTKGUOGP-UHFFFAOYSA-N 0.000 description 3
- FZBQWRFNMUYTAF-UHFFFAOYSA-N 5-[2,4-bis(trifluoromethyl)phenyl]-2-bromo-3-methoxycarbonylbenzoic acid Chemical compound COC(C(C=C(C=C1C(O)=O)C2=C(C(F)(F)F)C=C(C(F)(F)F)C=C2)=C1Br)=O FZBQWRFNMUYTAF-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- OZIPVCUSLMYWPW-UHFFFAOYSA-N 1-(4-iodophenyl)-2,4-bis(trifluoromethyl)benzene Chemical group FC(C(C=C1)=CC(C(F)(F)F)=C1C(C=C1)=CC=C1I)(F)F OZIPVCUSLMYWPW-UHFFFAOYSA-N 0.000 description 2
- OZAYOMJBHRYFOQ-UHFFFAOYSA-N 2-bromo-5-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=C(Br)C(C(O)=O)=C1 OZAYOMJBHRYFOQ-UHFFFAOYSA-N 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 2
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000000260 fractional sublimation Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229960002248 meradimate Drugs 0.000 description 2
- LTJIHUMXQFDNOQ-UHFFFAOYSA-N methyl 2-aminophenanthrene-3-carboxylate Chemical compound COC(C1=CC(C2=CC=CC=C2C=C2)=C2C=C1N)=O LTJIHUMXQFDNOQ-UHFFFAOYSA-N 0.000 description 2
- FQFGAKVKRXYHGB-UHFFFAOYSA-N methyl 3-aminoanthracene-2-carboxylate Chemical compound NC=1C(=CC2=CC3=CC=CC=C3C=C2C=1)C(=O)OC FQFGAKVKRXYHGB-UHFFFAOYSA-N 0.000 description 2
- AADQWLKBYLPJRG-UHFFFAOYSA-N methyl 3-aminophenanthrene-2-carboxylate Chemical compound NC=1C(=CC=2C=CC3=CC=CC=C3C2C1)C(=O)OC AADQWLKBYLPJRG-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- UZKBSZSTDQSMDR-UHFFFAOYSA-N 1-[(4-chlorophenyl)-phenylmethyl]piperazine Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)N1CCNCC1 UZKBSZSTDQSMDR-UHFFFAOYSA-N 0.000 description 1
- RLMFZHQMXHHHIO-UHFFFAOYSA-N 2-bromo-3-methoxycarbonyl-5-propan-2-ylbenzoic acid Chemical compound CC(C)C(C=C1C(O)=O)=CC(C(OC)=O)=C1Br RLMFZHQMXHHHIO-UHFFFAOYSA-N 0.000 description 1
- MZYCXRUBVGVHII-UHFFFAOYSA-N 2-iodo-5-propan-2-ylbenzoic acid Chemical group CC(C)c1ccc(I)c(c1)C(O)=O MZYCXRUBVGVHII-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- LTCYVXGIJJJJND-UHFFFAOYSA-N 4-(4-cyanoanilino)benzonitrile Chemical compound C1=CC(C#N)=CC=C1NC1=CC=C(C#N)C=C1 LTCYVXGIJJJJND-UHFFFAOYSA-N 0.000 description 1
- MBPCKEZNJVJYTC-UHFFFAOYSA-N 4-[4-(n-phenylanilino)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 MBPCKEZNJVJYTC-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- JRUIROTWKFAYJN-UHFFFAOYSA-N 4-n,4-n-diphenyl-1-n-[4-(n-phenylanilino)phenyl]benzene-1,4-diamine Chemical compound C=1C=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1NC(C=C1)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 JRUIROTWKFAYJN-UHFFFAOYSA-N 0.000 description 1
- HFPMNRKCIPGSNW-UHFFFAOYSA-N 4-propan-2-yl-n-(4-propan-2-ylphenyl)aniline Chemical compound C1=CC(C(C)C)=CC=C1NC1=CC=C(C(C)C)C=C1 HFPMNRKCIPGSNW-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940064734 aminobenzoate Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGFUDNJZHZNPCS-UHFFFAOYSA-N methyl 2-amino-5-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC(C(F)(F)F)=CC=C1N QGFUDNJZHZNPCS-UHFFFAOYSA-N 0.000 description 1
- XVICOGIQWUAIAV-UHFFFAOYSA-N methyl 2-amino-5-cyanobenzoate Chemical compound COC(=O)C1=CC(C#N)=CC=C1N XVICOGIQWUAIAV-UHFFFAOYSA-N 0.000 description 1
- XKERJVZDLDFKMI-UHFFFAOYSA-N methyl 2-iodo-5-(trifluoromethyl)benzoate Chemical compound COC(=O)c1cc(ccc1I)C(F)(F)F XKERJVZDLDFKMI-UHFFFAOYSA-N 0.000 description 1
- HENODHINIJTHDI-UHFFFAOYSA-N methyl 2-iodophenanthrene-3-carboxylate Chemical compound COC(C1=CC(C2=CC=CC=C2C=C2)=C2C=C1I)=O HENODHINIJTHDI-UHFFFAOYSA-N 0.000 description 1
- RMGHIDUPABRWTB-UHFFFAOYSA-N methyl 3-iodoanthracene-2-carboxylate Chemical compound COC(C1=CC2=CC3=CC=CC=C3C=C2C=C1I)=O RMGHIDUPABRWTB-UHFFFAOYSA-N 0.000 description 1
- KSUXKXHGXPKDMX-UHFFFAOYSA-N methyl 3-iodophenanthrene-2-carboxylate Chemical compound COC(C(C(I)=C1)=CC2=C1C1=CC=CC=C1C=C2)=O KSUXKXHGXPKDMX-UHFFFAOYSA-N 0.000 description 1
- SSXDDLXAVMYVKR-UHFFFAOYSA-N methyl 5-cyano-2-iodobenzoate Chemical compound COC(=O)C1=CC(C#N)=CC=C1I SSXDDLXAVMYVKR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VMVGVGMRBKYIGN-UHFFFAOYSA-N n-naphthalen-1-ylnaphthalen-1-amine Chemical compound C1=CC=C2C(NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 VMVGVGMRBKYIGN-UHFFFAOYSA-N 0.000 description 1
- QCOIZKZASBFCJG-UHFFFAOYSA-N n-phenylanthracen-1-amine Chemical compound C=1C=CC2=CC3=CC=CC=C3C=C2C=1NC1=CC=CC=C1 QCOIZKZASBFCJG-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/16—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a polycyclic aromatic compound, in particular to a triarylamine series derivative with a bridging structure and application thereof. The compound has a structure shown in a formula I or a formula II. When the compound is used as a luminescent layer material in an organic electroluminescent device, the luminous efficiency of the device can be effectively improved, the spectral color purity of the device can be improved, and the optimal technical effect of narrow luminous half-peak width of the device can be obtained.
Description
Technical Field
The invention relates to a polycyclic aromatic compound, in particular to a triarylamine series derivative with a bridging structure and application thereof, and particularly relates to application of the compound in an organic electroluminescent device.
Background
Over the last several decades, the field of Organic Light-Emitting Diodes (OLEDs) has made rapid progress, and has become one of the most promising technologies for full-color display and lighting applications. Compared with the traditional inorganic luminescent material, the organic luminescent material is more flexible in molecular design, various performance indexes such as thermal stability, luminescent property, electric conductivity and the like of molecules can be regulated and controlled by modifying and modifying a molecular structure, and meanwhile, many organic materials also have high luminescent quantum efficiency. In the aspect of display, OLEDs have the advantages of self-luminescence, wide color gamut, wide viewing angle, low response time, high blackness, flexible display realization and the like, and are known as a star flat display product in the 21 st century.
Unlike photoexcitation, only 25% of total excitons generated by electrons and holes injected from both the anode and the cathode under electrical excitation are singlet excitons, and the remaining 75% are triplet excitons. The most primitive OLEDs, which use conventional fluorescent materials, cannot utilize triplet excitons, which account for 75% of the total number of excitons, and thus their external quantum efficiency is often difficult to break through by 5%. In order to solve the triplet exciton utilization problem, second generation OLED materials have been developed since 1998, which are structurally characterized by transition metal complexes based on noble metals (e.g., iridium, platinum, osmium, etc.). Due to the heavy atom effect of the central noble metal, the material can effectively utilize triplet excitons, emit phosphorescence and realize 100% of exciton utilization rate. However, the cost of the noble metal used in the efficient phosphorescent material is high, the resource amount is small, and the long-term application is limited. Since 2011, professor Adachi at kyusha university of japan reported OLEDs based on purely organic Thermally Activated Delayed Fluorescence (TADF) materials. TADF materials can convert triplet excitons into singlet excitons by means of room temperature, thereby emitting delayed fluorescence, and thus achieving 100% exciton utilization. Therefore, the TADF material has a series of advantages of low cost and abundant sources, and is a third generation OLED material.
Meanwhile, the organic TADF material still faces many problems to be solved when it is practically applied to the display field. One of the most important is color purity. Recently, both gallium nitride based micro LEDs and CdS/ZnS based quantum dot LEDs achieve a-20 nm half-peak width (FWHM) in the blue region. In the case of organic light-emitting diodes, the half-width of their electroluminescence spectra is mostly above 40 nm. For TADF materials, the intrinsic strong charge transfer excited state property makes the half-peak width of the luminescence spectrum reach more than 60nm, which is very disadvantageous for commercial application. Even if commercial OLED display materials are recently realized, color filters or optical micro-cavities are added in practical use to improve the luminescent color purity under electroluminescence. However, at the same time, these methods inevitably bring about a loss of energy and an increase in cost. Therefore, there is an urgent need to design organic electroluminescent materials with high color purity and high efficiency to realize true high-quality full-color OLEDs. On the other hand, the stability of the material is crucial to the life of the corresponding OLED, and the use of a high-stability light-emitting material or the improvement of the stability of the light-emitting material is beneficial to the realization of a long-life OLED.
Disclosure of Invention
The invention aims to solve the problem that in the prior art, the number of high-color-purity high-efficiency luminescent materials is small, and provides a polycyclic aromatic compound, in particular a triarylamine derivative with a bridging structure.
The invention provides a polycyclic aromatic compound, the structure of which is shown as the following formula I or formula II:
in the formula I and the formula II, Ar1 ring, Ar2 ring, Ar3 ring, Ar4 ring, Ar5 ring and Ar6 ring respectively and independently represent one of substituted or unsubstituted C6-C60 monocyclic aryl or fused ring aryl, substituted or unsubstituted C4-C60 monocyclic heteroaryl or fused ring heteroaryl;
when substituents are present on the above-mentioned Ar1 ring, Ar2 ring, Ar3 ring, Ar4 ring, Ar5 ring, Ar6 ring, the substituents are independently selected from deuterium, halogen, cyano or the following groups: substituted or unsubstituted C1-C36 chain alkyl, substituted or unsubstituted C1-C36 chain alkenyl, substituted or unsubstituted C1-C36 chain alkynyl, substituted or unsubstituted C3-C36 cycloalkyl, substituted or unsubstituted C4-C36 cycloalkenyl, substituted or unsubstituted C36-C36 cycloalkynyl, substituted or unsubstituted C36 alkoxy-substituted or unsubstituted C36 alkoxy, C36-C36 thioalkoxy, carbonyl, carboxyl, nitro, amino, substituted or unsubstituted C36-C36 arylamino, substituted or unsubstituted C36-C36 heteroarylamino, substituted or unsubstituted C36-C36 monocyclic aryl, substituted or unsubstituted C36-C36 fused ring heteroaryl, substituted or unsubstituted C36-C36 monocyclic heteroaryl, substituted or unsubstituted C36-C36 fused ring condensed ring 36-C36 condensed ring heteroaryl, when each of the above-mentioned substituted or unsubstituted groups has a substituent, the substituent is selected from one or a combination of plural kinds of halogen, chain alkyl of C1 to C30, cycloalkyl of C3 to C30, alkenyl of C2 to C30, alkoxy or thioalkoxy of C1 to C30, cyano, nitro, carbonyl, carboxyl, amino, aryl of C6 to C30, and heteroaryl of C3 to C30.
Preferably, in formula i, the Ar1 ring, Ar2 ring, Ar3 ring are each independently selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl, tetracenyl, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl group;
further preferably, in formula i, the Ar1 ring is selected from substituted or unsubstituted phenyl, and the Ar2 ring and the Ar3 ring are each independently selected from one of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group or a carbazolyl group.
Preferably, in formula ii, the Ar4 ring, Ar5 ring and Ar6 ring are each independently selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl, tetracenyl, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl group;
further preferably, in formula ii, the Ar4 ring is selected from substituted or unsubstituted phenyl, and the Ar5 ring and the Ar6 ring are each independently selected from one of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group or a carbazolyl group.
Further, in formula i and formula ii, the Ar1 ring, Ar2 ring, Ar3 ring, and Ar4 ring are each independently selected from any one of the structures represented by formulae D1 to D298 below:
wherein,
represents the site of attachment to the nitrogen atom of the structure of formula I or IILRepresents a site of attachment to a bridging group to the left of the C-N bond in the structure of formula I or formula IIRRepresents a linking site with a bridging group to the right of the C-N bond in the structure of formula I or formula II;
in formula II, the Ar5 ring and the Ar6 ring are each independently selected from any one of the structures shown in formulas E1 to E612:
wherein,
represents the site of attachment to the nitrogen atom of the structure of formula II,. represents the site of attachment to the bridging group of the structure of formula II;
in the structural formula, when only one substituent group with variable positions and numbers is contained in the formula, the n represents 1 to the maximum allowable number of the substituent groups; when two substituent groups with variable positions and numbers are contained in the structural formula, m and n represent 0 to the maximum allowable number of the substituent groups and are not 0 simultaneously; when three substituent groups with variable positions and numbers are contained in the structural formula, m, l and n represent 0 to the maximum allowable number of the substituent groups, and are not 0 at the same time.
Still further preferably, in formula i and formula ii, the Ar1 ring, Ar2 ring, Ar3 ring, and Ar4 ring are each independently selected from any one of the structures shown below:
in formula ii, the Ar5 and Ar6 rings are each independently selected from any one of the structures shown below:
still more preferably, in formula i, the Ar2 ring and Ar3 ring structures are the same; in the formula II, the Ar5 ring and the Ar6 ring are the same in structure.
Further preferably, when a substituent is present on the ring Ar1, ring Ar2, ring Ar3 in formula I above or the ring Ar4, ring Ar5, ring Ar6 in formula ii above, said substituent is independently selected from deuterium or the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, 2, 2-dicyanovinyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, tetrabenzyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecylinyl, spirotrimeric indenyl, spiroisotridecylindenyl, spiroisotridecylinyl, Furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, kanilino, benzoxazolyl, naphthoxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzpyridazinyl, pyrimidinyl, benzopyrimidinyl, etc, Quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylanilino, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silyl, cyano, fluoro, chloro.
In the present specification, the expression of Ca to Cb represents that the group has carbon atoms a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified. In the structural formulae disclosed in the present specification, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.
The heteroatom in the present specification is generally referred to as being selected from N, O, S, P, Si and Se, preferably from N, O, S.
In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, and the like.
In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.
Further, based on the general structures of formula I and formula II, Table 1 and Table 2 respectively list representative compounds M1-M2239 of the present invention as specific preferred structural compounds of the general compounds of the present invention. It should be noted that the preferred compounds of the present invention are not limited to the structural schemes of the compounds listed in the following tables.
Table 1: partially preferred structural compounds based on the general formula I
Table 2: partially preferred structural compounds based on the general formula II
Further, the polycyclic aromatic compound of the present invention may preferably be a compound having a specific structure represented by C1 to C100, and these compounds are merely representative and do not limit the scope of the present invention.
The preparation process of the compound is simple and easy to implement, the raw materials are easy to obtain, and the compound is suitable for mass production amplification and is very suitable for industrial application.
The use of the above-mentioned compounds of the invention as functional materials in organic electronic devices comprising: an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or electronic paper, preferably an organic electroluminescent device.
The present invention also provides an organic electroluminescent device comprising a substrate, a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by any one of the general formulae I and II of the present invention, and more preferably comprises a specific compound listed in any one of tables 1 and 2.
Specifically, embodiments of the present invention provide an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; among them, the light-emitting layer preferably contains the compound of the general formula of the present invention represented by any one of the general formulae I and II. More preferably, the light-emitting layer contains a specific compound listed in any one of table 1 and table 2.
The specific reason why the compound of the formula I or formula ii of the present invention can further achieve excellent technical effects is not clear, and the specific reason why the compound of the present invention is excellent in the performance as a material for a light-emitting layer in an organic electroluminescent device is not clear, and the following is the presumption of the inventors, but these presumptions do not limit the scope of the present invention.
The triarylamine series derivatives with bridging structures designed by the invention have excellent bipolar transmission performance because of the nitrogen atoms for electron donor and the bridging groups for electron withdrawing. Meanwhile, the compound has stronger rigidity of molecular structure, can effectively inhibit the vibration and rotation of molecules, and reduces the recombination energy, thereby showing narrower full width at half maximum (FWHM) and lower nonradiative transition rate. The triarylamine series derivative with the bridging structure is applied to an organic electroluminescent device, and high-efficiency luminescence with high color purity can be obtained.
The organic electroluminescent device adopting the triarylamine series derivatives with the bridging structure as the luminescent layer material has the excellent technical effects of high luminescent efficiency, high spectral color purity and narrow half-peak width.
Drawings
FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum and a fluorescence spectrum of a compound M290 prepared in Synthesis example 2 of the present invention;
FIG. 2 is a graph showing an electroluminescence spectrum of an organic electroluminescent device OLED2 prepared in device example 2 of the present invention;
fig. 3 is an external quantum efficiency-current density curve of an organic electroluminescent device OLED2 device prepared according to device example 2 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Compound synthesis embodiments:
the specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.
Compounds of synthetic methods not mentioned in the examples of the present invention are all starting products obtained commercially. The solvents and reagents used in the present invention, such as ethyl acetate, toluene, sodium carbonate and other chemical reagents, can be purchased from domestic chemical product markets, such as from national drug group reagent company, TCI company, shanghai Bide medicine company, Bailingwei reagent company, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
Examples of Synthesis of Compounds
Representative synthetic route 1:
this representative synthetic route can be used for the synthesis of compound M1-M289 and preferably compound C1-C12.
Synthesis example 1: synthesis of Compound C1
In this synthesis example, compound C1 was synthesized according to the following scheme.
Methyl 2.49g (15mmol) of methyl 2-aminobenzoate, 9.12g (33mmol) of methyl 2-iodobenzoate, 4.98g (36mmol) of potassium carbonate, and 0.39g (6mmol) of activated copper powder were successively charged into a 250mL three-necked flask, followed by 150mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 180 ℃ for 96 hours under a closed condition. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 4:1 (volume ratio). Column chromatography gave 4.8g of a yellow solid in 69.3% yield.
4.8g (11.4mmol) of the obtained intermediate and 2.28g (57mmol) of sodium hydroxide were charged into a 250mL three-necked flask, followed by 120mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was heated under reflux and stirred under a closed condition for 24 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then the concentrated hydrochloric acid is used for acidification, so that a light yellow solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 3.9g of a yellow powder were obtained, representing a yield of 90.6%.
3.78g (9mmol) of intermediate obtained in the previous step was dissolved in 120mL of ultra-dry dichloromethane and added to a 250mL three-necked flask, followed by 2.67mL (31.5mmol) of oxalyl chloride and three drops of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 3.63mL (31.5mmol) of stannic chloride was added and the reaction was continued under reflux for 6 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 3:1 (volume ratio). Column chromatography separation gave 1.6g of a yellow-green solid, 48.6% yield.
1.6g (4.95mmol) of the intermediate obtained in the previous step and 6.53g of malononitrile (99mmol) were added to a 250mL round-bottom flask, followed by 150mL of acetic anhydride. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux for 24 hours under a closed condition. After the reaction is completed, carrying out reduced pressure suction filtration when the reaction system is cooled to room temperature, and washing a filter cake by using a small amount of acetic anhydride to remove the excessive reactant malononitrile. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 2.2g of crude product was obtained, yield 95%. After purification of the crude product by fractional sublimation, 1.2g of red crystalline solid powder was obtained. MALDI-TOF-MS results: molecular ion peaks: 467.1. elemental analysis results: theoretical value: c, 77.08; h, 1.94; n, 20.98. Experimental values: c, 77.12; h, 1.96; n, 20.92.
Synthesis example 2: synthesis of Compound C2
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-iodobenzoate was replaced with 5-tert-butyl-2-iodobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 579.22. elemental analysis results: theoretical value: c, 78.74; h, 4.35; n, 16.91. Experimental values: c, 78.75; h, 4.33; n, 16.92.
Synthetic example 3: synthesis of Compound C3
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-iodobenzoate was replaced with 5-isopropyl-2-iodobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 551.19. elemental analysis results: theoretical value: c, 78.39; h, 3.84; n, 17.77. Experimental values: c, 78.38; h, 3.83; n, 17.79.
Synthetic example 4: synthesis of Compound C4
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate and methyl 2-iodobenzoate were exchanged for equal amounts of methyl 5-cyano-2-aminobenzoate and methyl 5-cyano-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 542.08. elemental analysis results: theoretical value: c, 73.06; h, 1.11; n, 25.82. Experimental values: c, 73.05; h, 1.10; n, 25.84.
Synthesis example 5: synthesis of Compound C5
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate and methyl 2-iodobenzoate were exchanged for equal amounts of methyl 5-trifluoromethyl-2-aminobenzoate and methyl 5-trifluoromethyl-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 671.05. elemental analysis results: theoretical value: c, 59.03; h, 0.90; f, 25.47; n, 14.60. Experimental values: c, 59.04; h, 0.91; f, 25.46; n, 14.59.
Synthetic example 6: synthesis of Compound C6
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate and methyl 2-iodobenzoate were exchanged for the same amounts of methyl 3 ', 5' -bistrifluoromethyl-4-amino-3-bibenzoate and methyl 3 ', 5' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 1103.11. elemental analysis results: theoretical value: c, 58.76; h, 1.37; f, 30.98; and N, 8.88. Experimental values: c, 58.76; h, 1.35; f, 30.99; and N, 8.89.
Synthetic example 7: synthesis of Compound C7
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2 '-aminobenzoate and methyl 2' -iodobenzoate were exchanged for the same amount of methyl 2 ', 4' -bistrifluoromethyl-4-amino-3-bibenzoate and methyl 2 ', 4' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 1103.11. elemental analysis results: theoretical value: c, 58.76; h, 1.37; f, 30.98; and N, 8.88. Experimental values: c, 58.78; h, 1.37; f, 30.97; and N, 8.87.
Synthesis example 8: synthesis of Compound C8
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate was changed to 5-carbazolyl-2-aminobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 632.15. elemental analysis results: theoretical value: c, 79.74; h, 2.55; n, 17.71. Experimental values: c, 79.73; h, 2.54; n, 17.73.
Synthetic example 9: synthesis of Compound C9
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate was changed to methyl 4' -carbazolyl-4-amino-3-bibenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 708.18. elemental analysis results: theoretical value: c, 81.35; h, 2.84; n, 15.81. Experimental values: c, 81.34; h, 2.82; n, 15.83.
Synthetic example 10: synthesis of Compound C10
This example is substantially the same as synthetic example 1 except that: in this case, methyl 2-aminobenzoate was changed to 5-dianilino-2-aminobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 634.17. elemental analysis results: theoretical value: c, 79.49; h, 2.86; n, 17.66. Experimental values: c, 79.48; h, 2.88; n, 17.65.
Synthetic example 11: synthesis of Compound C11
This example is substantially the same as synthetic example 1 except that: in this example, methyl 2-aminobenzoate was replaced with an equivalent amount of methyl 4' -diphenylamino-4-amino-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 710.20. elemental analysis results: theoretical value: c, 81.11; h, 3.12; n, 15.77. Experimental values: c, 81.13; h, 3.11; n, 15.76.
Synthetic example 12: synthesis of Compound C12
This example is substantially the same as synthetic example 1 except that: in this case, methyl 2-aminobenzoate was exchanged for an equivalent amount of methyl 5- (9, 9-dimethylazepinyl) -2-aminobenzoate. MALDI-TOF-MS results: molecular ion peaks: 674.20. elemental analysis results: theoretical value: c, 80.11; h, 3.29; n, 16.61. Experimental values: c, 80.12; h, 3.30; n, 16.59.
Representative synthetic route 2:
this representative synthetic route can be used for the synthesis of compound M290-M2239 and preferably compound C13-C100.
Synthetic example 13: synthesis of Compound C13
In this synthesis example, compound C13 was synthesized according to the following scheme.
2.05g (7.5mmol) of methyl 2-bromoisophthalate, 1.36g (8mmol) of diphenylamine, 1.25g (9mmol) of potassium carbonate and 0.19g (3mmol) of activated copper powder were successively charged into a 100mL three-necked flask, followed by addition of 50mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and the mixture was refluxed at 180 ℃ under a closed condition for 48 hours. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:1 (volume ratio). Column chromatography gave 2.2g of a pale yellow-green oily liquid in 81% yield.
1.8g (5mmol) of the obtained intermediate and 1g (25mmol) of sodium hydroxide were charged into a 100mL three-necked flask, followed by addition of 50mL of a 50% volume fraction aqueous ethanol solution. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux at elevated temperature under a closed condition for 12 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then the concentrated hydrochloric acid is used for acidification, so that a light yellow solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 1.5g of a pale yellow powder was obtained, with a yield of 90%.
1.34g (4mmol) of the intermediate obtained in the previous step was dissolved in 40mL of ultra-dry dichloromethane and added to a 100mL three-necked flask, followed by 0.8mL (9.4mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.0mL (8.8mmol) of stannic chloride was added and the reaction was continued under reflux for 3 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 3:1 (volume ratio). Column chromatography separation gave 0.9g of a yellow-green solid in 75% yield.
0.8g (2.7mmol) of the intermediate obtained in the previous step and 3.56g of malononitrile (54mmol) were added to a 250mL round-bottom flask, followed by 100mL of acetic anhydride. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux for 24 hours under a closed condition. After the reaction is completed, carrying out reduced pressure suction filtration when the reaction system is cooled to room temperature, and washing a filter cake by using a small amount of acetic anhydride to remove the excessive reactant malononitrile. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 1.01g of crude product was obtained, yield 95%. After the crude product was purified by fractional sublimation, 0.5g of red crystalline solid powder was obtained. MALDI-TOF-MS results: molecular ion peaks: 393.1. elemental analysis results: theoretical value: c, 79.38; h, 2.82; and N, 17.80. Experimental values: c, 79.42; h, 2.85; n, 17.74.
Synthesis example 14: synthesis of Compound C14
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and di (4-tert-butylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 561.29. elemental analysis results: theoretical value: c, 81.25; h, 6.28; n, 12.47. Experimental values: c, 81.26; h, 6.29; n, 12.45.
Synthetic example 15: synthesis of Compound C15
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of di (4-t-butylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 505.23. elemental analysis results: theoretical value: c, 80.77; h, 5.38; and N, 13.85. Experimental values: c, 80.75; h, 5.39; and N, 13.86.
Synthetic example 16: synthesis of Compound C16
This example is substantially the same as synthetic example 13 except that: in this case, methyl 2-bromoisophthalate and diphenylamine were exchanged with equal amounts of methyl 5-isopropyl-2-bromoisophthalate and di (4-isopropylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 519.24. elemental analysis results: theoretical value: c, 80.90; h, 5.63; and N, 13.48. Experimental values: c, 80.91; h, 5.64; n, 13.46.
Synthetic example 17: synthesis of Compound C17
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of bis (4-isopropylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 477.20. elemental analysis results: theoretical value: c, 80.48; h, 4.85; n, 14.66. Experimental values: c, 80.47; h, 4.84; n, 14.67.
Synthetic example 18: synthesis of Compound C18
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of bis (4-trifluoromethylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 529.08. elemental analysis results: theoretical value: c, 63.53; h, 1.71; f, 21.53; n, 13.23. Experimental values: c, 63.54; h, 1.72; f, 21.52; and N, 13.22.
Synthetic example 19: synthesis of Compound C19
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of 4- [ (4-cyanophenyl) amino ] benzonitrile. MALDI-TOF-MS results: molecular ion peaks: 443.09. elemental analysis results: theoretical value: c, 75.84; h, 2.05; n, 22.11. Experimental values: c, 75.83; h, 2.04; n, 22.13.
Synthesis example 20: synthesis of Compound C20
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for bis (2 ', 4' -bistrifluoromethyl) biphenyl-4-amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 817.11. elemental analysis results: theoretical value: c, 61.70; h, 1.85; f, 27.88; and N, 8.57. Experimental values: c, 61.72; h, 1.86; f, 27.86; n, 8.56.
Synthetic example 21: synthesis of Compound C21
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for bis (3 ', 5' -bistrifluoromethyl) biphenyl-4-amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 817.11. elemental analysis results: theoretical value: c, 61.70; h, 1.85; f, 27.88; and N, 8.57. Experimental values: c, 61.71; h, 1.84; f, 27.86; and N, 8.59.
Synthetic example 22: synthesis of Compound C22
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and bis (4-trifluoromethylphenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 585.14. elemental analysis results: theoretical value: c, 65.64; h, 2.93; f, 19.47; n, 11.96. Experimental values: c, 65.65; h, 2.94; f, 19.46; n, 11.96.
Synthetic example 23: synthesis of Compound C23
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with methyl 5-tert-butyl-2-bromoisophthalate and bis (2 ', 4' -bistrifluoromethyl) biphenyl-4-amine in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 873.18. elemental analysis results: theoretical value: c, 63.24; h, 2.65; f, 26.09; and N, 8.02. Experimental values: c, 63.25; h, 2.65; f, 26.07; and N, 8.03.
Synthetic example 24: synthesis of Compound C24
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with methyl 5-tert-butyl-2-bromoisophthalate and bis (3 ', 5' -bistrifluoromethyl) biphenyl-4-amine in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 873.18. elemental analysis results: theoretical value: c, 63.24; h, 2.65; f, 26.09; and N, 8.02. Experimental values: c, 63.23; h, 2.65; f, 26.08; and N, 8.04.
Synthetic example 25: synthesis of Compound C25
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with equal amounts of methyl 4-bromo-2 ', 4' -bistrifluoromethyl-3, 5-biphenyldicarboxylate and bis (2 ', 4' -bistrifluoromethyl) biphenyl-4-amine. MALDI-TOF-MS results: molecular ion peaks: 1029.12. elemental analysis results: theoretical value: c, 58.32; h, 1.66; f, 33.21; and N, 6.80. Experimental values: c, 58.31; h, 1.65; f, 33.22; and N, 6.82.
Synthetic example 26: synthesis of Compound C26
This example is substantially the same as synthetic example 13 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with equal amounts of methyl 4-bromo-3 ', 5' -bistrifluoromethyl-3, 5-biphenyldicarboxylate and bis (3 ', 5' -bistrifluoromethyl) biphenyl-4-amine. MALDI-TOF-MS results: molecular ion peaks: 1029.12. elemental analysis results: theoretical value: c, 58.32; h, 1.66; f, 33.21; and N, 6.80. Experimental values: c, 58.33; h, 1.65; f, 33.22; n, 6.79.
Synthetic example 27: synthesis of Compound C27
This example is substantially the same as synthetic example 13 except that: in this example, diphenylamine is replaced with bis (4-carbazolylphenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 723.22. elemental analysis results: theoretical value: c, 82.97; h, 3.48; and N, 13.55. Experimental values: c, 82.99; h, 3.47; n, 13.54.
Synthetic example 28: synthesis of Compound C28
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of bis (4-diphenylaminophenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 727.25. elemental analysis results: theoretical value: c, 82.51; h, 4.02; and N, 13.47. Experimental values: c, 82.49; h, 4.03; and N, 13.48.
Synthetic example 29: synthesis of Compound C29
This example is substantially the same as synthetic example 13 except that: in this example, diphenylamine is replaced with the bis (4' -carbazolyl) biphenyl-4-amine in an equal amount. MALDI-TOF-MS results: molecular ion peaks: 875.28. elemental analysis results: theoretical value: c, 85.01; h, 3.80; n, 11.19. Experimental values: c, 85.00; h, 3.81; n, 11.20.
Synthetic example 30: synthesis of Compound C30
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is replaced by an equivalent amount of bis (4' -diphenylamino) biphenyl-4-amine. MALDI-TOF-MS results: molecular ion peaks: 879.31. elemental analysis results: theoretical value: c, 84.62; h, 4.24; n, 11.14. Experimental values: c, 84.60; h, 4.25; n, 11.15.
Synthetic example 31: synthesis of Compound C31
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine was exchanged for bis (4' - (9, 9-dimethylazepinyl)) biphenyl-4-amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 959.37. elemental analysis results: theoretical value: c, 85.06; h, 4.72; n, 10.21. Experimental values: c, 85.05; h, 4.71; n, 10.23.
Synthetic example 32: synthesis of Compound C32
This example is substantially the same as synthetic example 13 except that: in this example, diphenylamine is exchanged for the equivalent amount of 4' -carbazolyl-N-phenyl-4-benzidine. MALDI-TOF-MS results: molecular ion peaks: 634.19. elemental analysis results: theoretical value: c, 83.26; h, 3.49; and N, 13.24. Experimental values: c, 83.25; h, 3.48; and N, 13.26.
Synthetic example 33: synthesis of Compound C33
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for 4' -diphenylamino-N-phenyl-4-benzidine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 636.21. elemental analysis results: theoretical value: c, 83.00; h, 3.80; and N, 13.20. Experimental values: c, 83.02; h, 3.79; n, 13.19.
Synthesis example 34: synthesis of Compound C34
In this synthesis example, compound C34 was synthesized according to the following scheme.
1.61g (8mmol) of methyl 3-amino-2-naphthoate, 2.63g (8mmol) of methyl 3-iodo-2-naphthoate, 1.39g (10mmol) of potassium carbonate, and 0.25g (4mmol) of activated copper powder were sequentially charged into a 100mL three-necked flask, followed by 50mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and the mixture was stirred under reflux at 160 ℃ for 48 hours under a closed condition. After the reaction is completed, when the reaction system is cooled to room temperature, the obtained reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 1:4 (volume ratio). Column chromatography gave 2.62g of a white powdery solid in 85% yield.
2.62g (6.8mmol) of the obtained intermediate, 1.43g (7mmol) of iodobenzene, 1.25g (9mmol) of potassium carbonate and 0.19g (3mmol) of activated copper powder were successively charged into a 100mL three-necked flask, followed by 50mL of o-dichlorobenzene. The atmosphere in the three-necked flask was replaced with nitrogen, and the mixture was stirred under reflux at 160 ℃ for 48 hours under a closed condition. After the reaction is completed, when the reaction system is cooled to room temperature, the obtained reaction liquid is subjected to vacuum filtration, and a filter cake is washed by a dichloromethane solvent. The solution obtained after filtration was collected and spin-evaporated to remove the solvent. And then carrying out column chromatography separation on the product after spin drying, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether is 1:1 (volume ratio). Column chromatography gave 2.57g of a pale yellow powdery solid in 82% yield.
2.54g (5.5mmol) of the obtained intermediate and 1.2g (30mmol) of sodium hydroxide were charged into a 100mL three-necked flask, followed by 50mL of an aqueous ethanol solution having a volume fraction of 50%. The gas in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux at elevated temperature under a closed condition for 12 hours. After the hydrolysis reaction is completed, the solvent amount of the reaction system is concentrated to about half, and then the concentrated hydrochloric acid is used for acidification, so that a light yellow solid is separated out. The precipitated solid was suction filtered under reduced pressure and the filter cake was washed with a large amount of deionized water. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 2.19g of a pale yellow powder are obtained, with a yield of 92%.
2.17g (5mmol) of the intermediate obtained in the previous step was dissolved in 40mL of ultra-dry dichloromethane and added to a 100mL three-necked flask, followed by 1.0mL (11.8mmol) of oxalyl chloride and one drop of ultra-dry DMF. And (3) carrying out nitrogen replacement on the gas in the three-neck flask, and heating the reaction system to reflux under the conditions of a closed environment and stirring. After refluxing for 0.5h, 1.25mL (11mmol) of stannic chloride was added and the reaction was continued under reflux for 3 h. After the reaction is completed, when the reaction system is cooled to room temperature, 1M sodium hydroxide aqueous solution is dropwise added into the reaction solution, and the pH value of the system is adjusted to be neutral. The reaction solution was extracted three times with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. And (3) carrying out column chromatography separation on the obtained crude product, wherein the used eluent and the mixture ratio are dichloromethane: petroleum ether was 3:1 (volume ratio). Column chromatography gave 1.39g of a yellow-green solid in 70% yield.
1.39g (3.5mmol) of the intermediate obtained in the previous step and 4.23g of malononitrile (70mmol) were added to a 250mL round-bottom flask, followed by 100mL of acetic anhydride. The atmosphere in the three-necked flask was replaced with nitrogen, and then the mixture was stirred under reflux for 24 hours under a closed condition. After the reaction is completed, carrying out reduced pressure suction filtration when the reaction system is cooled to room temperature, and washing a filter cake by using a small amount of acetic anhydride to remove the excessive reactant malononitrile. After washing, the filter cake was recovered and placed in a vacuum oven to dry overnight at 80 ℃. After drying, 1.57g of crude product was obtained, with a yield of 91%. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.74; h, 3.04; n, 14.21.
Synthetic example 35: synthesis of Compound C35
This example is substantially the same as synthetic example 34, except that: in this example, iodobenzene was replaced with equal amount of 4-tert-butyliodobenzene. MALDI-TOF-MS results: molecular ion peaks: 549.20. elemental analysis results: theoretical value: c, 83.04; h, 4.22; n, 12.74. Experimental values: c, 83.02; h, 4.23; n, 12.75.
Synthetic example 36: synthesis of Compound C36
This example is substantially the same as synthetic example 34, except that: in this case, diphenylamine is exchanged for an equivalent amount of di (2-naphthyl) amine. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.74; h, 3.04; n, 14.21.
Synthetic example 37: synthesis of Compound C37
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of di (1-naphthyl) amine. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.73; h, 3.05; n, 14.20.
Synthetic example 38: synthesis of Compound C38
This example is substantially the same as synthetic example 37 except that: in this example, iodobenzene was replaced with equal amount of 4-tert-butyliodobenzene. MALDI-TOF-MS results: molecular ion peaks: 549.20. elemental analysis results: theoretical value: c, 83.04; h, 4.22; n, 12.74. Experimental values: c, 83.02; h, 4.25; n, 12.73.
Synthetic example 39: synthesis of Compound C39
This example is substantially the same as synthetic example 37 except that: in this case, diphenylamine is exchanged for an equivalent amount of bis (4- (3, 5-bistrifluoromethylphenyl) -1-naphthyl) amine. MALDI-TOF-MS results: molecular ion peaks: 917.14. elemental analysis results: theoretical value: c, 65.44; h, 2.09; f, 24.84; and N, 7.63. Experimental values: c, 65.45; h, 2.10; f, 24.83; and N, 7.62.
Synthetic example 40: synthesis of Compound C40
This example is substantially the same as synthetic example 37 except that: in this case, diphenylamine is exchanged for an equivalent amount of bis (4- (2, 4-bistrifluoromethylphenyl) -1-naphthyl) amine. MALDI-TOF-MS results: molecular ion peaks: 917.14. elemental analysis results: theoretical value: c, 65.44; h, 2.09; f, 24.84; and N, 7.63. Experimental values: c, 65.43; h, 2.10; f, 24.83; and N, 7.64.
Synthesis example 41: synthesis of Compound C41
This example is substantially the same as synthetic example 37 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with methyl 5-tert-butyl-2-bromoisophthalate and bis (4- (3, 5-bistrifluoromethylphenyl) -1-naphthyl) amine in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 973.21. elemental analysis results: theoretical value: c, 66.60; h, 2.79; f, 23.41; and N, 7.19. Experimental values: c, 66.59; h, 2.78; f, 23.42; and N, 7.20.
Synthesis example 42: synthesis of Compound C42
This example is substantially the same as synthetic example 37 except that: in this example, methyl 2-bromoisophthalate and diphenylamine were exchanged with methyl 5-tert-butyl-2-bromoisophthalate and bis (4- (2, 4-bistrifluoromethylphenyl) -1-naphthyl) amine in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 973.21. elemental analysis results: theoretical value: c, 66.60; h, 2.79; f, 23.41; and N, 7.19. Experimental values: c, 66.61; h, 2.78; f, 23.42; and N, 7.18.
Synthetic example 43: synthesis of Compound C43
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were changed to methyl 3-amino-2-anthracenecarboxylate and methyl 3-iodo-2-anthracenecarboxylate in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 593.65. elemental analysis results: theoretical value: c, 84.98; h, 3.23; n, 11.80. Experimental values: c, 84.99; h, 3.24; n, 11.77.
Synthetic example 44: synthesis of Compound C44
This example is substantially the same as synthetic example 34, except that: in this case, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were exchanged for the same amount of methyl 3-amino-2-phenanthrenecarboxylate and methyl 3-iodo-2-phenanthrenecarboxylate. MALDI-TOF-MS results: molecular ion peaks: 593.65. elemental analysis results: theoretical value: c, 84.98; h, 3.23; n, 11.80. Experimental values: c, 84.97; h, 3.24; n, 11.78.
Synthetic example 45: synthesis of Compound C45
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were exchanged for equal amounts of methyl 2-amino-3-phenanthrenecarboxylate and methyl 2-iodo-3-phenanthrenecarboxylate. MALDI-TOF-MS results: molecular ion peaks: 593.65. elemental analysis results: theoretical value: c, 84.98; h, 3.23; n, 11.80. Experimental values: c, 84.98; h, 3.25; n, 11.77.
Synthesis example 46: synthesis of Compound C46
This example is substantially the same as synthetic example 13 except that: in this example, diphenylamine was exchanged for the bis (2-pyrenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 641.16. elemental analysis results: theoretical value: c, 86.10; h, 2.98; n, 10.91. Experimental values: c, 86.09; h, 2.99; n, 10.92.
Synthetic example 47: synthesis of Compound C47
This example is substantially the same as synthetic example 13 except that: in this example, diphenylamine was exchanged for the bis (1-pyrenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 641.16. elemental analysis results: theoretical value: c, 86.10; h, 2.98; n, 10.91. Experimental values: c, 86.12; h, 2.97; n, 10.90.
Synthetic example 48: synthesis of Compound C48
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate was replaced by 5-tert-butyl-2-bromoisophthalate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 697.23. elemental analysis results: theoretical value: c, 86.06; h, 3.90; n, 10.04. Experimental values: c, 86.07; h, 3.88; n, 10.05.
Synthetic example 49: synthesis of Compound C49
This example is substantially the same as synthetic example 47 except that: in this example, the bis (1-pyrenyl) amine was changed to bis (7-tert-butyl-1-pyrenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 753.29. elemental analysis results: theoretical value: c, 86.03; h, 4.68; and N, 9.29. Experimental values: c, 86.04; h, 4.66; and N, 9.30.
Synthetic example 50: synthesis of Compound C50
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate and bis (1-pyrenyl) amine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and bis (7-tert-butyl-1-pyrenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 809.35. elemental analysis results: theoretical value: c, 86.00; h, 5.35; and N, 8.65. Experimental values: c, 85.99; h, 5.34; n, 8.67.
Synthetic example 51: synthesis of Compound C51
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate was replaced by equal amounts of methyl 4-bromo-3 ', 5' -bistrifluoromethyl-3, 5-biphenyldicarboxylate. MALDI-TOF-MS results: molecular ion peaks: 853.17. elemental analysis results: theoretical value: c, 75.97; h, 2.48; f, 13.35; and N, 8.20. Experimental values: c, 75.96; h, 2.47; f, 13.36; n, 8.21.
Synthesis example 52: synthesis of Compound C52
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate and bis (1-pyrenyl) amine were replaced with equal amounts of methyl 4-bromo-3 ', 5' -bistrifluoromethyl-3, 5-biphenyldicarboxylate and bis (7-tert-butyl-1-pyrenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 965.30. elemental analysis results: theoretical value: c, 77.09; h, 3.86; f, 11.80; and N, 7.25. Experimental values: c, 77.08; h, 3.87; f, 11.79; and N, 7.26.
Synthetic example 53: synthesis of Compound C53
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate was replaced with methyl 4-bromo-2 ', 4' -bistrifluoromethyl-3, 5-biphenyldicarboxylate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 853.17. elemental analysis results: theoretical value: c, 75.97; h, 2.48; f, 13.35; and N, 8.20. Experimental values: c, 75.98; h, 2.47; f, 13.34; n, 8.21.
Synthetic example 54: synthesis of Compound C54
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate and bis (1-pyrenyl) amine were replaced with equal amounts of methyl 4-bromo-2 ', 4' -bistrifluoromethyl-3, 5-biphenyldicarboxylate and bis (7-tert-butyl-1-pyrenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 965.30. elemental analysis results: theoretical value: c, 77.09; h, 3.86; f, 11.80; and N, 7.25. Experimental values: c, 77.09; h, 3.88; f, 11.80; and N, 7.23.
Synthetic example 55: synthesis of Compound C55
This example is substantially the same as synthetic example 47 except that: in this example, the bis (1-pyrenyl) amine was changed to bis (6- (3, 5-bistrifluoromethyl) phenyl-1-pyrenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 1065.18. elemental analysis results: theoretical value: c, 69.87; h, 2.18; f, 21.39; and N, 6.57. Experimental values: c, 69.86; h, 2.19; f, 21.38; and N, 6.58.
Synthetic example 56: synthesis of Compound C56
This example is substantially the same as synthetic example 47 except that: in this example, the bis (1-pyrenyl) amine was changed to bis (6- (2, 4-bistrifluoromethyl) phenyl-1-pyrenyl) amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 1065.18. elemental analysis results: theoretical value: c, 69.87; h, 2.18; f, 21.39; and N, 6.57. Experimental values: c, 69.88; h, 2.19; f, 21.38; n, 6.56.
Synthetic example 57: synthesis of Compound C57
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate and bis (1-pyrenyl) amine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and bis (6- (3, 5-bistrifluoromethyl) phenyl-1-pyrenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 1121.24. elemental analysis results: theoretical value: c, 70.65; h, 2.79; f, 20.32; and N, 6.24. Experimental values: c, 70.64; h, 2.78; f, 20.33; and N, 6.25.
Synthetic example 58: synthesis of Compound C58
This example is substantially the same as synthetic example 47 except that: in this example, methyl 2-bromoisophthalate and bis (1-pyrenyl) amine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and bis (6- (2, 4-bistrifluoromethyl) phenyl-1-pyrenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 1121.24. elemental analysis results: theoretical value: c, 70.65; h, 2.79; f, 20.32; and N, 6.24. Experimental values: c, 70.66; h, 2.78; f, 20.33; and N, 6.23.
Synthetic example 59: synthesis of Compound C59
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were exchanged for methyl 3-amino-2-triphenylbenzoate and methyl 3-iodo-2-triphenylbenzoate in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 693.20. elemental analysis results: theoretical value: c, 86.56; h, 3.34; and N, 10.09. Experimental values: c, 86.58; h, 3.35; n, 10.06.
Synthesis example 60: synthesis of Compound C60
This example is substantially the same as synthetic example 59, except that: in this example, iodobenzene was replaced with equal amount of 4-tert-butyliodobenzene. MALDI-TOF-MS results: molecular ion peaks: 749.26. elemental analysis results: theoretical value: c, 86.49; h, 4.17; and N, 9.34. Experimental values: c, 86.47; h, 4.18; and N, 9.35.
Synthetic example 61: synthesis of Compound C61
This example is substantially the same as synthetic example 59, except that: in this example, iodobenzene was converted to equal amounts of 4' -iodo-3, 5-bistrifluoromethylbiphenyl. MALDI-TOF-MS results: molecular ion peaks: 905.20. elemental analysis results: theoretical value: c, 76.90; h, 2.78; f, 12.58; n, 7.73. Experimental values: c, 76.91; h, 2.79; f, 12.57; and N, 7.72.
Synthesis example 62: synthesis of Compound C62
This example is substantially the same as synthetic example 59, except that: in this example, iodobenzene was converted to equal amounts of 4' -iodo-2, 4-bistrifluoromethylbiphenyl. MALDI-TOF-MS results: molecular ion peaks: 905.20. elemental analysis results: theoretical value: c, 76.90; h, 2.78; f, 12.58; n, 7.73. Experimental values: c, 76.89; h, 2.77; f, 12.59; n, 7.74.
Synthetic example 63: synthesis of Compound C63
This example is substantially the same as synthetic example 59, except that: in this example, methyl 7- (3, 5-bistrifluoromethyl) phenyl-3-amino-2-triphenylbenzoate, methyl 7- (3, 5-bistrifluoromethyl) phenyl-3-iodo-2-triphenylbenzoate and 4-tert-butyliodobenzene were used in amounts equivalent to methyl 3-amino-2-triphenylbenzoate, methyl 3-iodo-2-triphenylbenzoate and iodobenzene. MALDI-TOF-MS results: molecular ion peaks: 1173.27. elemental analysis results: theoretical value: c, 71.61; h, 3.00; f, 19.42; and N, 5.97. Experimental values: c, 71.60; h, 2.99; f, 19.43; and N, 5.98.
Synthetic example 64: synthesis of Compound C64
This example is substantially the same as synthetic example 59, except that: in this example, methyl 7- (2, 4-bistrifluoromethyl) phenyl-3-amino-2-triphenylbenzoate, methyl 7- (2, 4-bistrifluoromethyl) phenyl-3-iodo-2-triphenylbenzoate and 4-tert-butyliodobenzene were used in amounts equivalent to that of methyl 3-amino-2-triphenylbenzoate, methyl 3-iodo-2-triphenylbenzoate and iodobenzene. MALDI-TOF-MS results: molecular ion peaks: 1173.27. elemental analysis results: theoretical value: c, 71.61; h, 3.00; f, 19.42; and N, 5.97. Experimental values: c, 71.62; h, 2.99; f, 19.43; and N, 5.96.
Synthetic example 65: synthesis of Compound C65
This example is substantially the same as synthetic example 59, except that: in this example, methyl 7- (3, 5-bistrifluoromethyl) phenyl-3-amino-2-triphenylbenzoate, methyl 7- (3, 5-bistrifluoromethyl) phenyl-3-iodo-2-triphenylbenzoate and 4' -iodo-3, 5-bistrifluoromethylbiphenyl were used in amounts equivalent to methyl 3-amino-2-triphenylbenzoate, methyl 3-iodo-2-triphenylbenzoate and iodobenzene. MALDI-TOF-MS results: molecular ion peaks: 1329.21. elemental analysis results: theoretical value: c, 66.83; h, 2.20; f, 25.71; and N, 5.27. Experimental values: c, 66.84; h, 2.21; f, 25.70; and N, 5.26.
Synthetic example 66: synthesis of Compound C66
This example is substantially the same as synthetic example 59, except that: in this example, methyl 7- (2, 4-bistrifluoromethyl) phenyl-3-amino-2-triphenylbenzoate, methyl 7- (2, 4-bistrifluoromethyl) phenyl-3-iodo-2-triphenylbenzoate and 4' -iodo-2, 4-bistrifluoromethylbiphenyl were used in amounts equivalent to methyl 3-amino-2-triphenylbenzoate, methyl 3-iodo-2-triphenylbenzoate and iodobenzene. MALDI-TOF-MS results: molecular ion peaks: 1329.21. elemental analysis results: theoretical value: c, 66.83; h, 2.20; f, 25.71; and N, 5.27. Experimental values: c, 66.84; h, 2.22; f, 25.69; and N, 5.25.
Synthetic example 67: synthesis of Compound C67
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for the equivalent amount of bis (3-fluoranthenyl) amine. MALDI-TOF-MS results: molecular ion peaks: 641.16. elemental analysis results: theoretical value: c, 86.10; h, 2.98; n, 10.91. Experimental values: c, 86.11; h, 2.99; n, 10.89.
Synthetic example 68: synthesis of Compound C68
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-iodo-2-naphthoate was changed to methyl 2-iodobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.12. elemental analysis results: theoretical value: c, 81.25; h, 2.95; n, 15.79. Experimental values: c, 81.23; h, 2.96; and N, 15.80.
Synthetic example 69: synthesis of Compound C69
This example is substantially the same as synthetic example 13 except that: in this case, carbazole is replaced by N-phenyl-2-naphthylamine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.12. elemental analysis results: theoretical value: c, 81.25; h, 2.95; n, 15.79. Experimental values: c, 81.26; h, 2.94; n, 15.77.
Synthesis example 70: synthesis of Compound C70
This example is substantially the same as synthetic example 13 except that: in this case, carbazole is replaced by N-phenyl-1-naphthylamine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 443.11. elemental analysis results: theoretical value: c, 81.25; h, 2.95; n, 15.79. Experimental values: c, 81.25; h, 2.97; n, 15.77.
Synthesis example 71: synthesis of Compound C71
This example is substantially the same as synthetic example 70, except that: in this example, methyl 2-bromoisophthalate was replaced by 5-tert-butyl-2-bromoisophthalate in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 499.18. elemental analysis results: theoretical value: c, 81.74; h, 4.24; n, 14.02. Experimental values: c, 81.72; h, 4.25; and N, 14.03.
Synthetic example 72: synthesis of Compound C72
This example is substantially the same as synthetic example 70, except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-naphthylamine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and N- (4-tert-butyl) phenyl-1-naphthylamine. MALDI-TOF-MS results: molecular ion peaks: 555.24. elemental analysis results: theoretical value: c, 82.14; h, 5.26; and N, 12.60. Experimental values: c, 82.12; h, 5.27; and N, 12.61.
Synthetic example 73: synthesis of Compound C73
This example is substantially the same as synthetic example 70, except that: in this example, N-phenyl-1-naphthylamine was replaced with N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -1-naphthylamine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 655.12. elemental analysis results: theoretical value: c, 69.62; h, 2.31; f, 17.39; n, 10.68. Experimental values: c, 69.62; h, 2.33; f, 17.38; n, 10.67.
Synthetic example 74: synthesis of Compound C74
This example is substantially the same as synthetic example 70, except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-naphthylamine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -1-naphthylamine. MALDI-TOF-MS results: molecular ion peaks: 711.19. elemental analysis results: theoretical value: c, 70.88; h, 3.26; f, 16.02; n, 9.84. Experimental values: c, 70.89; h, 3.24; f, 16.01; and N, 9.85.
Synthetic example 75: synthesis of Compound C75
This example is substantially the same as synthetic example 70, except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-naphthylamine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -4- (3, 5-bistrifluoromethylphenyl) -1-naphthylamine. MALDI-TOF-MS results: molecular ion peaks: 923.19. elemental analysis results: theoretical value: c, 65.01; h, 2.73; f, 24.68; and N, 7.58. Experimental values: c, 65.00; h, 2.75; f, 24.67; and N, 7.59.
Synthetic example 76: synthesis of Compound C76
This example is substantially the same as synthetic example 70, except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-naphthylamine were replaced with equal amounts of methyl 4-bromo-3 ', 5' -bistrifluoromethyl-3, 5-biphenyldicarboxylate and N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -4- (3, 5-bistrifluoromethylphenyl) -1-naphthylamine. MALDI-TOF-MS results: molecular ion peaks: 1079.14. elemental analysis results: theoretical value: c, 60.07; h, 1.77; f, 31.67; and N, 6.49. Experimental values: c, 60.06; h, 1.76; f, 31.68; and N, 6.50.
Synthetic example 77: synthesis of Compound C77
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of N-phenyl-1-anthracenamine. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.76; h, 3.05; n, 14.20.
Synthesis example 78: synthesis of Compound C78
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were replaced with methyl 3-amino-2-anthracenecarboxylate and methyl 2-iodobenzoate in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.77; h, 3.07; n, 14.17.
Synthetic example 79: synthesis of Compound C79
This example is substantially the same as Synthesis example 78 except that: in this example, methyl 2-iodobenzoate was replaced with equal amount of methyl 4-tert-butyl-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 549.20. elemental analysis results: theoretical value: c, 83.04; h, 4.22; n, 12.74. Experimental values: c, 83.06; h, 4.21; n, 12.73.
Synthetic example 80: synthesis of Compound C80
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for an equivalent amount of N-phenyl-1-phenanthrene amine. MALDI-TOF-MS results: molecular ion peaks: 493.12. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.75; h, 3.07; n, 14.17.
Synthetic example 81: synthesis of Compound C81
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were exchanged for the same amount of methyl 3-amino-2-phenanthrenecarboxylate and methyl 2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 493.13. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.74; h, 3.07; n, 14.20.
Synthetic example 82: synthesis of Compound C82
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were exchanged for equal amounts of methyl 2-amino-3-phenanthrenecarboxylate and methyl 2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 493.12. elemental analysis results: theoretical value: c, 82.75; h, 3.06; n, 14.19. Experimental values: c, 82.73; h, 3.07; n, 14.21.
Synthetic example 83: synthesis of Compound C83
This example is substantially the same as synthetic example 82 except that: in this example, methyl 2-iodobenzoate was replaced with equal amount of methyl 4-tert-butyl-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 549.20. elemental analysis results: theoretical value: c, 83.04; h, 4.22; n, 12.74. Experimental values: c, 83.02; h, 4.23; n, 12.75.
Synthesis example 84: synthesis of Compound C84
This example is substantially the same as synthetic example 82 except that: in this example, methyl 2-iodobenzoate and iodobenzene were exchanged for equal amounts of methyl 4-tert-butyl-2-iodobenzoate and 4-tert-butyliodobenzene. MALDI-TOF-MS results: molecular ion peaks: 605.26. elemental analysis results: theoretical value: c, 83.28; h, 5.16; n, 11.56. Experimental values: c, 83.26; h, 5.17; n, 11.57.
Synthetic example 85: synthesis of Compound C85
This example is substantially the same as synthetic example 82 except that: in this example, methyl 2-iodobenzoate was replaced with an equivalent amount of methyl 3 ', 5' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 705.14. elemental analysis results: theoretical value: c, 71.49; h, 2.43; f, 16.15; and N, 9.93. Experimental values: c, 71.48; h, 2.44; f, 16.14; and N, 9.94.
Synthetic example 86: synthesis of Compound C86
This example is substantially the same as synthetic example 82 except that: in this example, iodobenzene and methyl 2-iodobenzoate were exchanged with equal amounts of 4-tert-butyliodobenzene and methyl 3 ', 5' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 761.20. elemental analysis results: theoretical value: c, 72.53; h, 3.31; f, 14.96; and N, 9.19. Experimental values: c, 72.54; h, 3.35; f, 14.95; and N, 9.18.
Synthesis example 87: synthesis of Compound C87
This example is substantially the same as synthetic example 82 except that: in this example, iodobenzene and methyl 2-iodobenzoate were exchanged for equal amounts of 4 ' -iodo-3, 5-bistrifluoromethylbiphenyl and methyl 3 ', 5 ' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 917.14. elemental analysis results: theoretical value: c, 65.44; h, 2.09; f, 24.84; and N, 7.63. Experimental values: c, 65.43; h, 2.08; f, 24.85; and N, 7.64.
Synthetic example 88: synthesis of Compound C88
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for N-phenyl-2-pyrene amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 517.13. elemental analysis results: theoretical value: c, 83.55; h, 2.92; n, 13.53. Experimental values: c, 83.57; h, 2.93; n, 13.51.
Synthetic example 89: synthesis of Compound C89
This example is substantially the same as synthetic example 13 except that: in this case, diphenylamine is exchanged for N-phenyl-1-pyrene amine in an equivalent amount. MALDI-TOF-MS results: molecular ion peaks: 517.13. elemental analysis results: theoretical value: c, 83.55; h, 2.92; n, 13.53. Experimental values: c, 83.55; h, 2.91; n, 13.54.
Synthetic example 90: synthesis of Compound C90
This example is substantially the same as synthetic example 89 except that: in this example, N-phenyl-1-pyrene amine was changed to N- (4-tert-butyl) phenyl-1-pyrene amine in an equal amount. MALDI-TOF-MS results: molecular ion peaks: 573.20. elemental analysis results: theoretical value: c, 83.75; h, 4.04; n, 12.21. Experimental values: c, 83.74; h, 4.03; n, 12.23.
Synthetic example 91: synthesis of Compound C91
This example is substantially the same as synthetic example 89 except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-pyrene amine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and N- (4-tert-butyl) phenyl-1-pyreneamine. MALDI-TOF-MS results: molecular ion peaks: 629.26. elemental analysis results: theoretical value: c, 83.92; h, 4.96; n, 11.12. Experimental values: c, 83.91; h, 4.95; n, 11.14.
Synthetic example 92: synthesis of Compound C92
This example is substantially the same as synthetic example 89 except that: in this example, N-phenyl-1-pyrene amine was changed to N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -1-pyrene amine in an equal amount. MALDI-TOF-MS results: molecular ion peaks: 729.14. elemental analysis results: theoretical value: c, 72.43; h, 2.35; f, 15.62; and N, 9.60. Experimental values: c, 72.42; h, 2.33; f, 15.64; and N, 9.61.
Synthetic example 93: synthesis of Compound C93
This example is substantially the same as synthetic example 89 except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-pyrene amine were replaced with equal amounts of methyl 5-tert-butyl-2-bromoisophthalate and N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -1-pyreneamine. MALDI-TOF-MS results: molecular ion peaks: 785.20. elemental analysis results: theoretical value: c, 73.37; h, 3.21; f, 14.51; and N, 8.91. Experimental values: c, 73.36; h, 3.22; f, 14.52; and N, 8.90.
Synthetic example 94: synthesis of Compound C94
This example is substantially the same as synthetic example 89 except that: in this example, methyl 2-bromoisophthalate and N-phenyl-1-pyrene amine were replaced with equal amounts of methyl 3 ', 5' -bistrifluoromethyl-4-bromo-3, 5-biphenyldicarboxylate and N- (3 ', 5' -bistrifluoromethyl-4-biphenyl) -1-pyreneamine. MALDI-TOF-MS results: molecular ion peaks: 941.14. elemental analysis results: theoretical value: c, 66.32; h, 2.03; f, 24.21; n, 7.44. Experimental values: c, 66.33; h, 2.02; f, 24.20; and N, 7.45.
Synthetic example 95: synthesis of Compound C95
This example is substantially the same as synthetic example 34, except that: in this example, methyl 3-amino-2-naphthoate and methyl 3-iodo-2-naphthoate were replaced with methyl 3-amino-2-triphenylbenzoate and methyl 2-iodobenzoate in equal amounts. MALDI-TOF-MS results: molecular ion peaks: 543.15. elemental analysis results: theoretical value: c, 83.96; h, 3.15; n, 12.88. Experimental values: c, 83.97; h, 3.13; n, 12.89.
Synthetic example 96: synthesis of Compound C96
This example is substantially the same as synthetic example 95 except that: in this example, methyl 2-iodobenzoate was replaced with equal amount of methyl 4-tert-butyl-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 599.21. elemental analysis results: theoretical value: c, 84.12; h, 4.20; n, 11.68. Experimental values: c, 84.12; h, 4.21; n, 11.67.
Synthetic example 97: synthesis of Compound C97
This example is substantially the same as synthetic example 95 except that: in this example, iodobenzene and methyl 2-iodobenzoate were exchanged with equal amounts of 4-tert-butyliodobenzene and methyl 4-tert-butyl-2-iodobenzoate. MALDI-TOF-MS results: molecular ion peaks: 655.27. elemental analysis results: theoretical value: c, 84.25; h, 5.07; n, 10.68. Experimental values: c, 84.23; h, 5.08; n, 10.69.
Synthetic example 98: synthesis of Compound C98
This example is substantially the same as synthetic example 95 except that: in this example, methyl 2-iodobenzoate was replaced with an equivalent amount of methyl 3 ', 5' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 755.15. elemental analysis results: theoretical value: c, 73.11; h, 2.53; f, 15.08; and N, 9.27. Experimental values: c, 73.10; h, 2.52; f, 15.09; and N, 9.28.
Synthetic example 99: synthesis of Compound C99
This example is substantially the same as synthetic example 95 except that: in this example, iodobenzene and methyl 2-iodobenzoate were exchanged with equal amounts of 4-tert-butyliodobenzene and methyl 3 ', 5' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 811.22. elemental analysis results: theoretical value: c, 73.98; h, 3.35; f, 14.04; and N, 8.63. Experimental values: c, 73.97; h, 3.36; f, 14.03; and N, 8.64.
Synthesis example 100: synthesis of Compound C100
This example is substantially the same as synthetic example 95 except that: in this example, iodobenzene and methyl 2-iodobenzoate were exchanged for equal amounts of 4 ' -iodo-3, 5-bistrifluoromethylbiphenyl and methyl 3 ', 5 ' -bistrifluoromethyl-4-iodo-3-bibenzoate. MALDI-TOF-MS results: molecular ion peaks: 967.16. elemental analysis results: theoretical value: c, 67.02; h, 2.19; f, 23.56; and N, 7.24. Experimental values: c, 67.03; h, 2.17; f, 23.55; and N, 7.26.
Application embodiments of the compounds prepared according to the invention:
the compound of the invention can be applied to an organic electroluminescent device, namely an OLED device, and is most preferably used as a material in a light-emitting layer.
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, inkjet printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylenes, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives.
The hole injection layer is positioned between the anode and the hole transport layer, and the hole injection layer can be a single compound material or a combination of a plurality of compounds.
The material of the light-emitting layer employed in the organic electroluminescent device of the present invention is selected from one of the preferred compounds M1-M2239 of the present invention.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: liq, LiF, NaCl, CsF, Li2O,Cs2CO3,BaO,Na,Li,Ca。
The technical effects and advantages of the present invention are demonstrated and verified by testing the practical use properties of the compounds of the present invention, particularly by applying the compounds of the present invention to organic electroluminescent devices.
The preparation process of the organic electroluminescent device comprises the following steps:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an isopropanol mixed solvent, baking in a clean environment until water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using a low-energy cationic beam;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, vacuum evaporating a hole injection layer on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 5-10 nm; vacuum evaporating a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 60-80 nm; the luminescent layer of the vacuum evaporation device on the hole transport layer comprises a main material and a dye materialThe material is selected from one of the compounds C1, C13, C34, C36, C37, C43, C44, C45, C46, C47, C59 and C67, the evaporation rate of the host material is adjusted to 0.1nm/s, the evaporation rate of the dye in the luminescent layer is adjusted to 3%, and the total thickness of the luminescent layer evaporated is 30 nm. Vacuum evaporating an electron transport layer material of the device on the luminescent layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30-60 nm; LiF with the thickness of 1nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The OLED device is tested in an integrating sphere under room temperature and atmospheric conditions, and parameters such as voltage, external quantum efficiency, current density, brightness and the like of the device can be measured through an absolute external quantum efficiency measuring system C9920-12 of Hamamatsu company, Japan, and a prepared Hamamatsu C10027-02 type PMA-12 photon multi-channel spectrometer (the detection range is 350-.
The following devices, OLED1 to OLED12, using the compounds C1, C13, C34, C36, C37, C43, C44, C45, C46, C47, C59 and C67 of the present invention were prepared according to the above-described step methods.
The structure of each OLED device and the thickness of each layer are respectively as follows:
device embodiment 1 of the invention:
when the compound C1 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C1 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device embodiment 2 of the invention:
when the compound C13 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C13 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 3 of the invention:
when the compound C34 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C34 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 4 of the invention:
when the compound C36 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C36 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 5 of the invention:
when the compound C37 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C37 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 6 of the present invention:
when the compound C43 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C43 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 7 of the present invention:
when the compound C44 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C44 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 8 of the present invention:
when the compound C45 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C45 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 9 of the present invention:
when the compound C46 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C46 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 10 of the present invention:
when the compound C47 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C47 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 11 of the present invention:
when the compound C59 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C59 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Device example 12 of the present invention:
when the compound C67 is used as a luminescent material, the device structure is as follows: ITO/HATCN (10nm)/NPB (70nm)/TCTA (10nm)/3 wt% C67 TBPi (30nm)/TPBi (60nm)/LiF (1nm)/Al (150nm), device performance tests were performed according to the organic electroluminescent device test method described above.
Comparative device example 1:
using compound QAO of the present prior art as the light emitting material, the device structure was: ITO/HATCN (10nm)/TAPC (45nm)/TCTA (10nm)/5 wt% QAO mCP (20nm)/B4PyPPM (40nm)/Liq (2nm)/Al (120nm), and device performance tests were carried out according to the organic electroluminescent device test method described above.
Specific data on the performance of each of the organic electroluminescent devices prepared as described above are listed in table 3 below.
Table 3:
the details of the performance of the organic electroluminescent device prepared in example 2 are specifically shown in fig. 2 and fig. 3, where fig. 2 is the electroluminescent spectrum of the device OLED2, and fig. 3 is the current density-external quantum efficiency curve of the device OLED 2.
As can be seen from the performance comparison results of the device embodiments prepared by the invention, the organic electroluminescent device prepared by adopting the preferred compound has the advantages of high luminous efficiency, high spectral color purity, narrow half-peak width and the like, and simultaneously realizes the characteristic of large-amplitude red shift. The analysis of the specific reasons is as follows: due to the existence of the bridging group for electron withdrawing and the nitrogen atom for electron donating in the molecule of the compound and the rigid structure of the molecule, the compound has bipolar transmission performance, higher luminescent color purity and higher efficiency in electroluminescent devices.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A polycyclic aromatic compound having a structure represented by formula I or formula II:
in the formula I and the formula II, Ar1 ring, Ar2 ring, Ar3 ring, Ar4 ring, Ar5 ring and Ar6 ring respectively and independently represent one of substituted or unsubstituted C6-C60 monocyclic aryl or fused ring aryl, substituted or unsubstituted C4-C60 monocyclic heteroaryl or fused ring heteroaryl;
when the substituent groups are present on the Ar1 ring, the Ar2 ring, the Ar3 ring, the Ar4 ring, the Ar5 ring, and the Ar6 ring, the substituent groups are independently selected from deuterium, halogen, cyano, or the following groups: substituted or unsubstituted C1-C36 chain alkyl, substituted or unsubstituted C1-C36 chain alkenyl, substituted or unsubstituted C1-C36 chain alkynyl, substituted or unsubstituted C3-C36 cycloalkyl, substituted or unsubstituted C4-C36 cycloalkenyl, substituted or unsubstituted C36-C36 ring alkynyl, substituted or unsubstituted C36-C36 alkoxy, substituted or unsubstituted C36-C36 thioalkoxy, carbonyl, carboxyl, nitro, amino, substituted or unsubstituted C36-C36 arylamino, substituted or unsubstituted C36-C36 heteroarylamino, substituted or unsubstituted C36-C36 monocyclic aryl, substituted or unsubstituted C36-C36 fused ring heteroaryl, substituted or unsubstituted C36-C36 monocyclic heteroaryl, substituted or unsubstituted C36 fused ring heteroaryl, substituted or unsubstituted C36-C36 fused ring condensed ring heteroaryl, when each of the above-mentioned substituted or unsubstituted groups has a substituent, the substituent is selected from one or a combination of plural kinds of halogen, chain alkyl of C1 to C30, cycloalkyl of C3 to C30, alkenyl of C2 to C30, alkoxy or thioalkoxy of C1 to C30, cyano, nitro, carbonyl, carboxyl, amino, aryl of C6 to C30, and heteroaryl of C3 to C30.
2. The polycyclic aromatic compound of claim 1, wherein when the substituent is present on the Ar1, Ar2, Ar3, Ar4, Ar5, Ar6 rings, the substituent is independently selected from deuterium or the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, 2, 2-dicyanovinyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, tetrabenzyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecylinyl, spirotrimeric indenyl, spiroisotridecylindenyl, spiroisotridecylinyl, Furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, kanilino, benzoxazolyl, naphthoxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzpyridazinyl, pyrimidinyl, benzopyrimidinyl, etc, Quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylanilino, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silyl, cyano, fluoro, chloro.
3. Polycyclic aromatic compound according to claim 1 or 2, wherein in formula I, the ring Ar1 isThe Ar2 ring and the Ar3 ring are each independently selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl, tetracenyl, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl group;
in formula II, the Ar4 ring, the Ar5 ring and the Ar6 ring are respectively and independently selected from one of the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group or a carbazolyl group.
4. The polycyclic aromatic compound of claim 1 or 2, wherein in formula i, the Ar1 ring is selected from substituted or unsubstituted phenyl, and the Ar2 ring and Ar3 ring are each independently selected from one of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl, tetracenyl, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl or carbazolyl group;
in the formula II, the Ar4 ring is selected from substituted or unsubstituted phenyl, and the Ar5 ring and the Ar6 ring are respectively and independently selected from substituted or unsubstituted groupsOne of (1): phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
A phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group or a carbazolyl group.
5. The polycyclic aromatic compound of claim 1, wherein in formula i and formula ii, the Ar1, Ar2, Ar3 and Ar4 rings are each independently selected from any one of the structures represented by formulae D1 to D298 below:
wherein,
represents the site of attachment to the nitrogen atom of the structure of formula I or IILRepresents a site of attachment to a bridging group to the left of the C-N bond in the structure of formula I or formula IIRRepresents a linking site with a bridging group to the right of the C-N bond in the structure of formula I or formula II;
in formula II, the Ar5 ring and the Ar6 ring are each independently selected from any one of the structures shown in formulas E1 to E612:
wherein,
represents the site of attachment to the nitrogen atom of the structure of formula II,. represents the site of attachment to the bridging group of the structure of formula II;
in the structural formula, when only one substituent group with variable positions and numbers is contained in the formula, the n represents 1 to the maximum allowable number of the substituent groups; when two substituent groups with variable positions and numbers are contained in the structural formula, m and n respectively represent 0 to the maximum allowable number of the substituent groups and are not 0 at the same time; when three substituent groups with variable positions and numbers are contained in the structural formula, m, l and n respectively represent 0 to the maximum allowable number of the substituent groups and are not 0 at the same time.
6. The polycyclic aromatic compound of claim 1, wherein in formula i and formula ii, the Ar1 ring, Ar2 ring, Ar3 ring, and Ar4 ring are each independently selected from any one of the structures shown below:
in the above-mentioned structural formula, the compound,
represents the site of attachment to the nitrogen atom of the structure of formula I or IILRepresents a site of attachment to a bridging group to the left of the C-N bond in the structure of formula I or formula IIRRepresents a linking site with a bridging group to the right of the C-N bond in the structure of formula I or formula II;
in formula ii, the Ar5 and Ar6 rings are each independently selected from any one of the structures shown below:
in the above structural formula, n represents 1 to the maximum allowable number of substituents.
7. The polycyclic aromatic compound according to any one of claims 3 to 6, wherein in formula I, the Ar2 ring and the Ar3 ring are the same;
in the formula II, the Ar5 ring and the Ar6 ring are the same in structure.
8. The polycyclic aromatic compound of claim 1, wherein the compound of formula I or formula ii is a compound having the following specific structure:
9. use of the polycyclic aromatic compound of any one of claims 1 to 8 as a functional material in an organic electronic device comprising: an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet type scanner, or electronic paper.
10. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010681028.1A CN113943290A (en) | 2020-07-15 | 2020-07-15 | Polycyclic aromatic compound and application thereof in electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010681028.1A CN113943290A (en) | 2020-07-15 | 2020-07-15 | Polycyclic aromatic compound and application thereof in electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113943290A true CN113943290A (en) | 2022-01-18 |
Family
ID=79325858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010681028.1A Pending CN113943290A (en) | 2020-07-15 | 2020-07-15 | Polycyclic aromatic compound and application thereof in electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113943290A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253396A (en) * | 2020-03-13 | 2020-06-09 | 杨曦 | Organic compound, mixture, composition, high polymer and application |
| CN111606906A (en) * | 2020-06-19 | 2020-09-01 | 苏州久显新材料有限公司 | Polycyclic nitrogen-containing compound and electronic device |
-
2020
- 2020-07-15 CN CN202010681028.1A patent/CN113943290A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253396A (en) * | 2020-03-13 | 2020-06-09 | 杨曦 | Organic compound, mixture, composition, high polymer and application |
| CN111606906A (en) * | 2020-06-19 | 2020-09-01 | 苏州久显新材料有限公司 | Polycyclic nitrogen-containing compound and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110407858B (en) | Novel compound, application thereof and organic electroluminescent device using compound | |
| JP5524344B2 (en) | Novel condensed ring compound and organic electronic device using the same | |
| CN101331111B (en) | New anthracene derivant, its preparation method and use the organic electronic light emitting device of this derivative | |
| CN110467536A (en) | Nitrogenous compound, organic electroluminescence device and photoelectric conversion device | |
| CN111153919A (en) | Luminescent material, application thereof and organic electroluminescent device comprising luminescent material | |
| KR20110027635A (en) | New heterocyclic derivatives and organic light emitting device using the same | |
| KR20100119077A (en) | New compounds and organic electronic device using the same | |
| CN111647009A (en) | Boron-containing compound and electronic device thereof | |
| CN113788852A (en) | Luminescent material, application thereof and organic electroluminescent device comprising luminescent material | |
| JP2008201716A (en) | Material for organic light-emitting element and organic light-emitting element using the same | |
| CN111892607B (en) | N-heterobiphenyl organic compound and application thereof | |
| CN112778343A (en) | Boron-based organic electroluminescent material and preparation method and application thereof | |
| CN116836193A (en) | Organic compound, application thereof and organic electroluminescent device comprising same | |
| CN117024459A (en) | Organic compound and application thereof | |
| CN112442037B (en) | Luminescent material and application thereof | |
| CN112174968A (en) | Organic compound for light-emitting device, application thereof, and organic electroluminescent device | |
| CN111769199B (en) | Novel organic electroluminescent device | |
| CN111303157A (en) | Naphthopyrazine derivative, preparation method thereof and electronic device | |
| CN115703747A (en) | Organic compound having spirofluorene structure for light emitting device, organic electroluminescent device | |
| CN115160342A (en) | Compound, application thereof and organic electroluminescent device comprising compound | |
| CN113943287B (en) | Polycyclic aromatic compound and application thereof in electroluminescent device | |
| CN113943290A (en) | Polycyclic aromatic compound and application thereof in electroluminescent device | |
| CN113620817A (en) | Compound and application thereof | |
| CN113880848A (en) | Compound, application thereof and organic electroluminescent device comprising compound | |
| CN113121407A (en) | Compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220118 |
|
| WD01 | Invention patent application deemed withdrawn after publication |