CN115626914A - 一种咔唑类化合物及其应用 - Google Patents
一种咔唑类化合物及其应用 Download PDFInfo
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- CN115626914A CN115626914A CN202211376213.5A CN202211376213A CN115626914A CN 115626914 A CN115626914 A CN 115626914A CN 202211376213 A CN202211376213 A CN 202211376213A CN 115626914 A CN115626914 A CN 115626914A
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- substituted
- carbazole
- oled device
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 64
- -1 Carbazole compound Chemical class 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims description 68
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 12
- 229910052805 deuterium Inorganic materials 0.000 claims description 12
- 125000004431 deuterium atom Chemical group 0.000 claims description 12
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000005493 quinolyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims description 3
- 230000005525 hole transport Effects 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000005551 pyridylene group Chemical group 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 125000006738 (C6-C20) heteroaryl group Chemical group 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002019 doping agent Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 9
- 150000001716 carbazoles Chemical class 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
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- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 6
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 238000006887 Ullmann reaction Methods 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 150000001499 aryl bromides Chemical class 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- 238000010485 C−C bond formation reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- RRCMGJCFMJBHQC-UHFFFAOYSA-N (2-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Cl RRCMGJCFMJBHQC-UHFFFAOYSA-N 0.000 description 1
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000006835 (C6-C20) arylene group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-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
- NXYICUMSYKIABQ-UHFFFAOYSA-N 1-iodo-4-phenylbenzene Chemical group C1=CC(I)=CC=C1C1=CC=CC=C1 NXYICUMSYKIABQ-UHFFFAOYSA-N 0.000 description 1
- HNZUKQQNZRMNGS-UHFFFAOYSA-N 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound BrC1=CC=CC(C=2N=C(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HNZUKQQNZRMNGS-UHFFFAOYSA-N 0.000 description 1
- CBJHFGQCHKNNJY-UHFFFAOYSA-N 4-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2Br CBJHFGQCHKNNJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- 229940125773 compound 10 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical group C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
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- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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Abstract
本发明提供一种咔唑类化合物及其应用。所述咔唑类化合物具有如式I所示结构。本发明通过对咔唑类化合物的结构进行设计,使其适用作OLED器件中发光层的主体材料,以此制备得到的OLED器件具有较低的驱动电压、较高的电流效率和较长的寿命。
Description
技术领域
本发明属于有机电致发光材料技术领域,具体涉及一种咔唑类化合物及其应用。
背景技术
有机发光OLED器件是一种多层叠加的半导体发光二极管,其中的发光层一般由发光掺杂剂和主体材料构成。主体材料约占据发光层材料重量百分含量的98-80%,对OLED器件的发光效率、寿命、启动电压等有重要影响。作为磷光三线态或TADF(热活化延迟荧光,Thermally Activated Delayed Fluorescence)OLED主体材料,除了要求其三线态(T1)>2.45eV之外,要求承载电子与空穴注入、传输功能外,并且还要稳定持续时间以保证器件工作寿命。
咔唑或其衍生物是OLED有机发光器件常用的主体材料,但是现有技术中提供的咔唑类化合物或其衍生物中常常具有萘基或苯并菲基,导致其三线态较小,且由此制备得到的OLED器件的性能较差。因此,本领域亟待开发更多种类、更高性能的发光层主体材料,以制备得到各项性能优异的OLED器件。
发明内容
针对现有技术的不足,本发明的目的在于提供一种咔唑类化合物及其应用。本发明中,通过对咔唑类化合物的结构进行设计,使其具有较好的电子与空穴双注入能力,适用作OLED器件中发光层的主体材料,且以此制备得到的OLED器件具有较低的驱动电压、较高的电流效率和较长的寿命。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供一种咔唑类化合物,所述咔唑类化合物具有如式I所示结构:
其中,Z1-Z4各自独立地选自C原子或N原子;
A选自取代或未取代的C6~C30芳基、取代或未取代的C2~C30杂芳基中的任意一种;
X、Y、R1和R2各自独立地选自氢原子、氘原子、取代或未取代的C1-C10直链或支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6~C30芳基、取代或未取代的C2~C30杂芳基、中的任意一种,其中,波浪线表示连接位点;
R1可以与Z1、Z2稠合成环,R1可以与Z3、Z4稠合成环;
Ra和Rb各自独立地选自取代或未取代的C1~C30烷基、取代或未取代的C6~C30芳基、取代或未取代的C2~C30的芳杂基中的任意一种;
A、X、Y、R1、R2、Ra和Rb中所述取代的取代基各自独立地选自氘原子、氟原子、C1-C5烷基、C6~C20芳基、C6~C20杂芳基中的至少一种。
本发明中,通过对咔唑类化合物的具体结构进行设计,进一步通过设计咔唑类化合物中含有适当的吸电功能基团(例如吡啶基、三嗪基),使其具有较好的电子与空穴双注入能力,同时使咔唑类化合物的三线态T1>2.45eV,适用作OLED发光层主体材料,且由此制备得到的OLED器件具有较低的驱动电压、较高的电流效率和较长的寿命。
本发明中,所述C6~C30可以是C6、C8、C10、C12、C18、C20、C24、C28或C30等。
所述C2~C30可以是C3、C5、C8、C10、C16、C20、C24或C30等。
所述C1~C10可以是C1、C2、C4、C6、C7或C10等。
所述C3~C10可以是C3、C4、C5、C6、C7、C8、C9或C10。
所述C1~C30可以是C1、C2、C5、C7、C10、C12、C15、C18、C20、C22、C25、C27或C30等。
所述C1~C5可以是C1、C2、C3、C4或C5。
所述C6~C320可以是C6、C8、C10、C12、C18或C20等。
以下作为本发明的优选技术方案,但不作为对本发明提供的技术方案的限制,通过以下优选的技术方案,可以更好的达到和实现本发明的目的和有益效果。
作为本发明的优选技术方案,所述A选自如下基团中的任意一种:
其中,Ar选自氢原子、苯基、萘基、联苯基、吡啶基、联吡啶基、喹啉基、咔唑基、二苯并呋喃基、二苯并噻吩基、4,6-二苯基-1,3,5-三嗪基中的任意一种;
Rc选自氢原子或苯基;
a选自1~4的整数(例如可以是1、2、3、4),优选为1或2;
波浪线表示连接位点。
作为本发明的优选技术方案,所述A选自如下基团中的任意一种:
其中,波浪线表示连接位点。
作为本发明的优选技术方案,所述Ra和Rb各自独立地选自苯基、联苯基、9,9-二甲基芴基中的任意一种。
作为本发明的优选技术方案,所述X和Y各自独立地选自氢原子、氘原子、苯基、萘基、9,9-二甲基芴基、噻吩基、吡咯基、呋喃基、苯并噻吩基、苯并呋喃基、二苯并噻吩基、二苯并呋喃基、咔唑基、4,6-二苯基-1,3,5-三嗪基、 中的任意一种;
其中,波浪线表示连接位点。
作为本发明的优选技术方案,所述式I所示咔唑类化合物选自如下化合物C1~C96中的任意一种:
需要说明的是,本发明中对于式I所示咔唑类化合物的制备方法不做任何特殊的限定,本领域常用的制备方法均适用,例如C-C键形成可采用钯催化下铃木Suzucki反应或路易斯酸Lewis Acid催化下的Friedel-Crafts反应;C-N键形成可采用碘化亚铜催化下的乌尔曼Ullmann反应、钯催化下只需要弱碱的Buchwald偶联反应、钯催化下的芳基三氟甲磺酸酯与芳胺的反应、使用强碱如CsOH催化下芳溴与仲胺反应等。
本发明中对于上述部分式I所示咔唑类化合物的制备方法进行下述说明,其他式I所示咔唑类化合物均可参照下述方法制备得到:
化合物C24的合成路线如下:
化合物C34的合成路线如下:
化合物C53的合成路线如下:
优选地,所述式I所示咔唑类化合物选自如下化合物中的任意一种:
第二方面,本发明提供一种OLED器件,所述OLED器件包括依次叠加设置的阴极、电子注入层、电子传输层、发光层、空穴传输层、空穴注入层和阳极;
所述发光层的主体材料包括如第一方面所示的式I所示咔唑类化合物。
优选地,所述发光层的主体材料包括如第一方面所述的化合物C1~C96中的任意一种或两种的组合。
本发明中,通过对式I所示咔唑类化合物的结构进行设计,使其具有电子与空穴双注入能力,可单独作为绿光OLED发光层主体材料,制备OLED器件。为了进一步提高OLED器件的性能,并配合不同种类的发光层掺杂剂,制备到性能优异的OLED器件,也可以选用两种均具有式I所示咔唑类化合物,同时作为发光层主体材料,构成双主体,制备OLED器件。
作为本发明的优选技术方案,所述OLED器件为绿光OLED器件、红光OLED器件或荧光OLED器件。
优选地,所述OLED器件为绿光OLED器件。
本发明提供的式I所示咔唑类化合物可以作为红光、绿光OLED器件或TADF发光材料的主体材料用以制备相应OLED器件,优先选择式I所示咔唑类化合物作为绿光OLED器件发光层的主体材料。
本发明中,式I所示咔唑类化合物可单独作为发光层主体材料使用,也可以选用两种具有式I所示咔唑类化合物,同时作为发光层主体材料,制备OLED器件。为了进一步提高OLED器件的性能,适应不同的发光层掺杂剂,本发明中式I所示咔唑类化合物更优选应用是与其他主体材料共同使用,进一步增强发光层的电荷传输能力和电荷注入能力,由此提高OLED器件的电流效率和寿命。
作为本发明的优选技术方案,所述发光层的主体材料还包括二咔唑类化合物和/或三嗪类化合物;
所述二咔唑类化合物具有如式II所示结构:
其中,L选自单键、C6~C20亚芳基或C4~C20亚杂芳基中的任意一种;
Ar1、Ar2、Ar3、Ar4各自独立地选自氢原子、氘原子、-CN、取代或未取代的C6~C20芳基、C3~C20杂芳基中的任意一种;
Ar1与Ar3所在咔唑基之间可以通过单键连接成环;
Ar2与Ar4所在咔唑基之间可以通过单键连接成环。
优选地,所述L选自单键、亚苯基或亚吡啶基中的任意一种。
优选地,所述C6~C20芳基选自苯基、联苯基、萘基、9,9-二甲基芴基基中的任意一种。
优选地,所述C3~C20杂芳基选自吡啶基、二苯并呋喃基、二苯并噻吩基中的任意一种。
优选地,所述式II所示二咔唑类化合物选自如下化合物B1~B72中的任意一种:
本发明中,对化合物B1~B72的合成方法,不做任何特殊的限定,本领域适用的方法均可用于制备化合物B1~B70,示例性地包括但不限于:例如C-C键形成可采用钯催化下铃木Suzucki反应或路易斯酸Lewis Acid催化下的Friedel-Crafts反应;C-N键形成可采用碘化亚铜催化下的乌尔曼Ullmann反应、钯催化下只需要弱碱的Buchwald偶联反应、钯催化下的芳基三氟甲磺酸酯与芳胺的反应、使用强碱如CsOH催化下芳溴与仲胺反应等;具体合成方法例子可参考KR20180012499A。部分氘代化合物可以使用氘代原料,或是最终化合物在氘代水与酸性催化剂下获得。
所述三嗪类化合物具有如式III所示结构:
m选自0或1;
L1、L2各自独立地选自单键、亚苯基、亚萘基或亚吡啶基中的任意一种;
R1、R2、R3、R4各自独立地选自氢原子、氘原子、苯基、萘基、芴基、喹啉基、吡啶基、呋喃基、噻吩基、二苯并噻吩基、二苯并呋喃基、咔唑基中的任意一种;
Ar5选自苯基、联苯基、二苯并呋喃基、二苯并噻吩基中的任意一种。
优选地,R1、R2、R3、R4各自独立地选自氢原子、苯基、、二苯并呋喃基、二苯并噻吩基中的任意一种。
优选地,所述式III所示三嗪类化合物选自如下化合物A-1~A-116中的任意一种:
本发明中,式III所示三嗪类化合物具有电负性较强的三嗪环,以式III所示三嗪类化合物和式I所示咔唑类化合物共同作为发光层的主体材料,可提高发光层的电荷注入能力,进一步提高OLED器件的性能。
本发明中,对化合物A-1~A-116的合成方法,不做任何特殊的限定,本领域适用的方法均可用于制备化合物A-1~A-112,示例性地包括但不限于:例如C-C键形成可采用钯催化下铃木Suzucki反应或路易斯酸Lewis Acid催化下的Friedel-Crafts反应;C-N键形成可采用碘化亚铜催化下的乌尔曼Ullmann反应、钯催化下只需要弱碱的Buchwald偶联反应、钯催化下的芳基三氟甲磺酸酯与芳胺的反应、使用强碱如CsOH催化下芳溴与仲胺反应等,具体合成可参考文献参考CN110540536A。氘代化合物制备可以使用氘代原料,或最终产物在氘代水与酸性催化下获得。
本发明中,所述发光层的材料还包括掺杂材料(掺杂剂),需要说明的是,本发明中对掺杂剂的选择没有特殊限制,本领域常用的绿光、黄光、红光掺杂剂均适用,示例性地包括但不限于:所述掺杂材料选自如下化合物中的任意一种:
第三方面,本发明提供一种如第一方面所述的OLED器件在OLED显示屏和照明器件中的应用。
本发明所述范畴还包括上述的化合物混合在有机发光器件(OLED有机发光二极管)的应用。当用作发光层时,为提高发光效率,有必要尽量避免发光分子的聚集,通常是使用小于50%的浓度发光(重量)材料,优选为1%~40%掺杂剂,掺到一个主体材料中。当然,主体材料也可以是多于一种材料的混合主体材料,此时量少者为辅助主体材料。图1为所述OLED器件结构示意图,发光层为104标号。图1所示OLED发光器件还可以组合成叠层OLED发光器件应用,此类叠层OLED发光器件可以是使用相同或不同主体材料与本发明所述的发光掺杂材料构成2个发光层器件或曰双栈窜联蓝光OLED器件(图2)。
与现有技术相比,本发明具有以下有益效果:
本发明中,通过对咔唑类化合物的结构进行设计,使其具有较好的电子与空穴双注入能力,且咔唑类化合物的三线态T1>2.45eV,适用作OLED器件中发光层的主体材料,且以此制备得到的OLED器件具有较低的驱动电压、较高的电流效率和较长的寿命。
附图说明
图1是本发明应用例1提供的OLED器件的结构示意图;
图2是由应用例1提供的OLED器件通过一层电荷产生层CGL连接得到的2个发光器件组合的示意图;
其中,100-基板、101-阳极、102-空穴注入层、103-空穴传输层、104-激子阻挡层、105-蓝光发光层、106-电子传输层、107-电子注入层、200-电荷层、201-空穴注入层、202-空穴传输层、203-激子阻挡层、204-蓝光发光层、205-电子传输层、206-电子注入层、207-阴极。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
合成例1
本合成例提供一种化合物C24及其合成方法,合成路线如下:
具体合成方法如下:
(1)在氮气氛围下,将4-溴-9H-咔唑(5g,20.3mmol),邻氯苯硼酸(3.2g,20.3mmol),Pd(dppf)Cl2(149mg,0.2mmol),K2CO3(5.6g,40.6mmol)溶于102mL四氢呋喃和34mL水的混合溶液中,回流反应4小时,反应完全后恢复至室温,过滤得到有机相,有机相经无水硫酸镁干燥后减压蒸馏,所得固体采用甲苯重结晶得化合物3(4.1g,收率为72%)。
(2)在氮气氛围下,将化合物3(4g,14.4mmol)、醋酸钯(32mg,0.14mmol)、三叔丁基膦(58mg,0.29mmol)、DBU(4.4g,28.8mmol)溶于96mL DMF中,回流反应6小时,反应完全后加水反沉淀得到产物粗品。粗品经甲苯重结晶得化合物4(2.6g,收率为75%)。
(3)将化合物4(2.5g,10.4mmol)溶解于50ml DMF中,随后将2.0g NBS(11.4mmol,溶解于19ml DMF中)于0℃下30分钟内逐滴加入到反应液中。反应完全后加水反沉淀得到产物粗品。粗品经甲苯重结晶得化合物5(2.8g,收率为85%)。
(4)在氮气氛围下,将化合物5(2.5g,7.8mmol),苯硼酸(1.0g,8.6mmol),Pd2(dba)3(72mg,0.08mmol),Cs2CO3(5.1g,15.6mmol)溶于21mL甲苯、14mL乙醇及7mL水的混合溶液中,回流反应4小时。反应完全后恢复至室温,过滤得到有机相。有机相经无水硫酸镁干燥后减压蒸馏,所得固体采用甲苯重结晶得化合物7(2.0g,收率为80%)。
(5)在氮气氛围下,将化合物7(2.0g,6.3mmol)、2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪(2.7g,6.9mmol)、Pd2(dba)3(58mg,0.06mmol)、三叔丁基膦(25mg,0.13mmol)、叔丁醇钠(1.2g,12.6mmol)溶于42mL二甲苯中,回流反应12小时,反应完全后恢复至室温,过滤得到有机相,有机相经无水硫酸镁干燥后减压蒸馏,所得固体柱色谱分离纯化得化合物C24(2.8g,收率为70%)。
化合物C24理论计算分子式C45H28N4,分子量为624.7;经质谱检验,其m/e=624。
合成例2
本合成例提供一种化合物C34及其合成方法,合成路线如下:
参考合成实施例1中的合成方法,将合成实施例1中的化合物8替换为等物质的化合物9,化合物C34(2g,收率为60%)。
化合物C34理论计算分子式C45H28N4,分子量为624.7;经质谱检验,其m/e=624。
合成例3
本合成例提供一种化合物C53及其合成方法,合成路线如下:
(1)参考合成实施例1中的合成方法,将合成实施例1中的化合物6替换为等物质的化合物10,得到化合物11(3.2g,产率为73%);
(2)在氮气氛围下,将化合物11(3.0g,6.22mmol)、4-碘联苯(2.09g,7.46mmol)、Pd(OAc)2(10mg,0.06mmol)、SPhos(77mg,0.19mmol)、叔丁醇钠(1.2g,12.6mmol)溶于40ml二甲苯中,90度反应12小时。反应完全后恢复至室温,过滤得到有机相。有机相经无水硫酸镁干燥后减压蒸馏,所得固体柱色谱分离纯化得化合物C53(2.8g,收率为72%)。
化合物C53理论计算分子式C48H30N2,分子量为634.8;经质谱检验,其m/e=634。
以上未列明的本发明其它化合物的合成方法,可以参照本领域公知常识和以上合成实施例进行,不再进行一一叙述。
对本发明提供的咔唑类化合物的性能进行表征,具体测试方法如下:
三线态(T1)能级:通过高斯DFT泛函理论计算进行计算,判断化合物的三线态(T1)能级是否大于2.45eV,
以C9化合物为例,经高斯DFT泛函理论计算结果为:HOMO=-5.61eV,LUMO=-2.95eV,单线态S1=437nm(2.84eV),三线态T1=466nm(2.66eV),其三线态能级大于绿光主体材料要求的T1>2.45eV,满足绿光三线态要求。
对化合物进行质谱检测,得到质荷比(m/z)。
测试结果如下表1所示:
表1
下述器件应用例中所采用的化合物的具体结构如下所示:
应用对比例中,使用的主体材料的结构式如下所示:
应用例1
本应用例提供一种绿光OLED器件,以本发明提供的咔唑类化合物C1~C96、二咔唑类化合物B1~B70或三嗪类化合物A-1~A-112中的至少一种化作为有机电致发光器件中的发光层的主体材料(Host),详见表3;
如图1所示,所述OLED器件包括依次叠加设置的阴极107、电子注入层(EIL)106、电子传输层(ETL)105、发光层(EML)104、空穴传输层(HTL)103、空穴注入层(HIL)102和阳极(ITO基片)101,在一个本底真空达10-5Pa的多源蒸发OLED制备设备中,制备得到所述OLED器件,所述OLED器件的制备方法过程中各有机层及电极的真空沉积速度于时间列于表2。
表2 OLED器件制备条件(发光层中掺杂wt浓度6%)
应用例2-28
应用例2-28分别提供一种绿光OLED器件,与应用例1的区别仅在于,发光层的主体材料不同(详见表3),其他条件与应用例1相同。
对比应用例1-4
对比应用例1-2提供一种绿光OLED器件,与应用例1的区别仅在于,发光层的主体材料不同(详见表3),其他条件与应用例1相同。
性能测试
使用大电流驱动OLED器件以加速老化寿命与光色性能分析系统测试以上提供的有机电致发光器件的驱动电压、电流效率和LT95。其中,电流效率是亮度为1000cd/m2对应的数值,LT95是指保持器件初始电流密度40mA/cm2不变,器件效率降为初始电流密度对应的效率的95%所需要的时间,单位是小时。具体测试结果如表3所示:
表3
由表3的内容可知,本发明中通过对咔唑类化合物的结构进行设计,使其具有较好的电子与空穴双注入能力,且咔唑类化合物的三线态T1>2.45eV,适用作绿光OLED器件中发光层的主体材料。
同时,本发明提供的式I所示咔唑类化合物可单独作为发光层主体材料使用,也可以与如式II所示二咔唑类化合物和/或式III所示三嗪类化合物共同作为发光层主体材料,以此制备得到的OLED器件具有较低的驱动电压、较高的电流效率和较长的寿命。
尤其,当选用本发明提供的化合物C10、化合物C49、化合物C56与式II所示二咔唑类化合物和/或式III所示三嗪类化合物形成的三元发光层材料后,可进一步提高OLED器件的性能及寿命。使用部分氘代的器件应用27、28表明,氘代多元主体材料,可获得额外的器件寿命提升。
应用例29-35
本应用例提供一种红光OLED器件,使用发光客体材料RPD-19作为掺杂剂(4%wt),以本发明提供的咔唑类化合物C1~C96、二咔唑类化合物B1~B70和三嗪类化合物A-1~A-112中的至少一种化作为有机电致发光器件中的发光层的三元主体材料(Host,详见表4)。
应用例29-35分别提供一种红光OLED器件,与应用对比例5的区别仅在于,发光层的主体材料不同(详见表4),其他条件与应用例1相同。
对比应用例5
对比应用例5提供一种红光OLED器件,与应用例27的区别仅在于,发光层的主体材料不同(详见表4),其他条件与应用例1相同。
对应用例5以及应用例29-35提供的红光OLED器件的性能进行测试,测试方法同上。具体测试结果如表4所示:
表4红光OLED器件(ELλmax=622nm)
由表4的内容可知,本发明中通过使用双主体材料,制备得到的红光OLED器件(应用例27)比已知双主体搭配效率提升约11%;使用三主体材料,制备OLED器件(应用例28-33),可进一步提高OLED器件的电流效率和寿命。
申请人声明,本发明通过上述实施例来说明本发明的详细工艺流程,但本发明并不局限于上述详细工艺流程,即不意味着本发明必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种咔唑类化合物,其特征在于,所述咔唑类化合物具有如式I所示结构:
其中,Z1-Z4各自独立地选自C原子或N原子;
A选自取代或未取代的C6~C30芳基、取代或未取代的C2~C30杂芳基中的任意一种;
X、Y、R1和R2各自独立地选自氢原子、氘原子、取代或未取代的C1-C10直链或支链烷基、取代或未取代的C3-C10环烷基、取代或未取代的C6~C30芳基、取代或未取代的C2~C30杂芳基、中的任意一种,其中,波浪线表示连接位点;
R1可以与Z1、Z2稠合成环,R1可以与Z3、Z4稠合成环;
Ra和Rb各自独立地选自取代或未取代的C1~C30烷基、取代或未取代的C6~C30芳基、取代或未取代的C2~C30的芳杂基中的任意一种;
A、X、Y、R1、R2、Ra和Rb中所述取代的取代基各自独立地选自氘原子、氟原子、C1-C5烷基、C6~C20芳基、C6~C20杂芳基中的至少一种。
4.根据权利要求1-3任一项所述的咔唑类化合物,其特征在于,所述Ra和Rb各自独立地选自苯基、联苯基、9,9-二甲基芴基中的任意一种。
7.一种OLED器件,其特征在于,所述OLED器件包括依次叠加设置的阴极、电子注入层、电子传输层、发光层、空穴传输层、空穴注入层和阳极;
所述发光层的主体材料包括如权利要求1-6任一项所述的式I所示咔唑类化合物;
优选地,所述发光层的主体材料包括如权利要求6所述的化合物C1~C96中的任意一种或两种的组合。
8.根据权利要求7所述的OLED器件,其特征在于,所述OLED器件为绿光OLED器件或红光OLED器件;
优选地,所述OLED器件为绿光OLED器件。
9.根据权利要求7或8所述的OLED器件,其特征在于,所述发光层的主体材料还包括二咔唑类化合物和/或三嗪类化合物;
所述二咔唑类化合物具有如式II所示结构:
其中,L选自单键、C6~C20芳基或C4~C20杂芳基中的任意一种;
Ar1、Ar2、Ar3、Ar4各自独立地选自氢原子、氘原子、-CN、取代或未取代的C6~C20芳基、取代或未取代的C3~C20杂芳基中的任意一种;
Ar1与Ar3所在咔唑基之间可以通过单键连接成环;
Ar2与Ar4所在咔唑基之间可以通过单键连接成环;
Ar3与Ar3所在苯环之间可以通过单键连接成环;
所述三嗪类化合物具有如式III所示结构:
m选自0或1;
L1、L2各自独立地选自单键、亚苯基、亚萘基或亚吡啶基中的任意一种;
R1-R4各自独立地选自氢原子、氘原子、苯基、萘基、芴基、喹啉基、吡啶基、呋喃基、噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基中的任意一种;
Ar5选自苯基、联苯基、二苯并呋喃基、二苯并噻吩基中的任意一种。
10.一种如权利要求7-9任一项所述的OLED器件在OLED显示屏和照明器件中的应用。
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