CN112010760B - 一种螺二芴类有机电致发光化合物及有机电致发光器件 - Google Patents
一种螺二芴类有机电致发光化合物及有机电致发光器件 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 72
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000005525 hole transport Effects 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 40
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000010410 layer Substances 0.000 description 32
- 239000000706 filtrate Substances 0.000 description 30
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 30
- 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 30
- 239000012074 organic phase Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 20
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- 229910052757 nitrogen Inorganic materials 0.000 description 20
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- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 15
- 229940125797 compound 12 Drugs 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- 238000001308 synthesis method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 239000012043 crude product Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 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 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- -1 N-ethylcarbazolyl Chemical group 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 3
- 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 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
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- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
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- GCWIQUVXWZWCLE-INIZCTEOSA-N pelabresib Chemical compound N([C@@H](CC(N)=O)C=1ON=C(C=1C1=CC=CC=C11)C)=C1C1=CC=C(Cl)C=C1 GCWIQUVXWZWCLE-INIZCTEOSA-N 0.000 description 2
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- 125000004306 triazinyl group Chemical group 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
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- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
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- SPDPTFAJSFKAMT-UHFFFAOYSA-N 1-n-[4-[4-(n-[4-(3-methyl-n-(3-methylphenyl)anilino)phenyl]anilino)phenyl]phenyl]-4-n,4-n-bis(3-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 SPDPTFAJSFKAMT-UHFFFAOYSA-N 0.000 description 1
- HVZMNJSQXYOADV-UHFFFAOYSA-N 2'-tert-butyl-1,1'-spirobi[fluorene] Chemical group C(C)(C)(C)C=1C2(C3=CC4=CC=CC=C4C3=CC1)C=CC=C1C3=CC=CC=C3C=C12 HVZMNJSQXYOADV-UHFFFAOYSA-N 0.000 description 1
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- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
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- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Abstract
本发明公开了一种螺二芴类有机电致发光化合物及有机电致发光器件，该螺二芴类有机电致发光化合物结构式如式I所示：
Description
技术领域
本发明属于有机电致发光材料技术领域，具体涉及一种螺二芴类有机电致发光化合物及有机电致发光器件。
背景技术
有机电致发光器件(Organic Light-emitting Devices,OLED)是利用如下原理的自发性发光器件：当施加电场时，荧光物质通过正极注入的空穴和负极注入的电子的重新结合而发光。这种自发光器件，具有电压低、亮度高、视角宽、响应快、温度适应性好等特性，并且超薄，能制作在柔性面板上等优点，广泛应用于手机、平板电脑、电视、照明等领域。
有机电致发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成有机电致发光器件。作为电流器件，当对有机电致发光器件的两端电极施加电压，并通过电场作用在有机层功能材料膜层中产生正负电荷，正负电荷进一步在发光层中复合，产生光，此过程为电致发光。
对于有机电致发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现有机电致发光器件性能的不断提升，不但需要有机电致发光器件的结构和制作工艺的创新，更需要有机电致光电功能材料的不断研究和创新，创制出更高性能的有机电致功能材料。
就当前有机电致发光产业的实际需求而言，目前有机电致发光材料的发展还远远不够，落后于面板制造企业的要求。
就目前现有技术US2017331039A1对比而言，本发明设计的材料由于在螺二芴上引入叔丁基，增大了材料分子的扭矩及自由度，降低了材料的平面性，进而降低材料的结晶性。材料分子的平面性降低能够有效提高材料的使用效果及使用范围。材料分子扭矩及自由度的增大有效改善了该类材料的空穴传输能力，调节了空穴传输材料的HOMO能级，进而大大降低了有机电致发光器件的驱动电压，有效较少能耗,并大幅度提高了有机电致发光器件的寿命。
发明内容
发明目的：针对上述技术问题，本发明提供了一种螺二芴类有机电致发光化合物及有机电致发光器件。
为了达到上述发明目的，本发明所采用的技术方案如下：
一种螺二芴类有机电致发光化合物，其结构式如下所示：
其中，Ar1、Ar2各自独立的选自取代或未取代的C6-C24芳香族烃基、取代或未取代的C5-C24杂芳香族烃基；
R1、R2、R3各自独立的选自氢、取代或未取代的C1-C4的直链或支链烷基、取代或未取代的C6-C18的芳香族烃基，取代或未取代的C5-C18杂芳香族烃基，且R1、R2、R3不同时为氢。
优选的，Ar1、Ar2各自独立的选自取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团；
R1、R2、R3各自独立的选自氢，取代或未取代的C1-C4的直链或支链烷基，取代或未取代的苯基及其衍生物基团，取代或未取代的萘基及其衍生物基团，取代或未取代的蒽基及其衍生物基团，取代或未取代的菲基及其衍生物基团，取代或未取代的芴基及其衍生物基团，取代或未取代的咔唑基及其衍生物基团，取代或未取代的呋喃基及其衍生物基团，取代或未取代的噻吩基及其衍生物基团，取代或未取代的嘧啶基及其衍生物基团，取代或未取代的吡啶基及其衍生物基团，取代或未取代的三嗪基及其衍生物基团。
进一步优选的，Ar1、Ar2各自独立的选自取代或未取代的苯基、苯甲基、苯乙基、萘基、蒽基、菲基、芴基、氧芴基、9,9-螺二芴基团、9,9-二甲基芴基团、9,9-二苯基芴基团、咔唑基、N-乙基咔唑基、4-羟基咔唑基、苯并咔唑基、呋喃基、噻吩基、苯基嘧啶基、嘧啶基、吡啶基、三嗪基；
R1、R2、R3各自独立的选自氢，取代或未取代的甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基、联苯基、9,9-二甲基芴基团，且R1、R2、R3不同时为氢。
进一步优选的，所述取代的取代基选自以下原子或基团中的至少一种：氘、羟基、氰基、单氘甲基、双氘甲基、三氘甲基、C1-C4的直链或支链烷基、C6-C18芳香族烃基、C5-C24杂芳香族烃基。
进一步优选的，Ar1、Ar2各自独自选自以下基团：
所述R1、R2、R3各自独自选自以下原子或基团：
且R1、R2、R3不同时为H。
进一步优选的，所述螺二芴有机电致发光化合物为下列结构式化合物中的一种：
本发明还提供了一种螺二芴类有机电致发光化合物的制备方法，包括以下步骤：
(1)惰性气体保护下将结构通式为
的化合物Ⅰ加入到无水THF中，降温至-78℃，滴加正丁基锂，化合物Ⅰ与正丁基锂的摩尔比为1:1.1，反应30-50min后，将将结构通式为
的化合物Ⅱ的无水THF溶液加入，-78℃下继续反应2-4h，淬灭后缓慢恢复室温加入二氯甲烷和水萃取分液，二氯甲烷相水洗，干燥，减压浓缩后柱层析提纯后得到结构通式为
的化合物Ⅲ；
(2)化合物Ⅲ在异丙醇和盐酸共沸的条件下反应后抽滤得到结构通式为
的化合物Ⅳ；
(3)惰性气体保护下，将化合物Ⅳ、结构通式为
的化合物Ⅴ、叔丁醇钠、Pd2(dba)3：三叔丁基膦按摩尔比1:1.1:1.1:0.05-0.06：0.01-0.06加入到甲苯中，加料完毕后升温至回流反应5-8h，反应完毕后降至室温后加水搅拌15-30min后过滤，滤液分液后得有机相，有机相干燥后浓缩柱层析提纯即可得到所述螺二芴类有机电致发光化合物。
上述的螺二芴类有机电致发光化合物在制备发光器件中的应用。
一种有机电致发光器件，包括阳极、空穴注入层、空穴传输层、电子阻隔层、发光层、空穴阻隔层、电子传输层、电子注入层和阴极，空穴传输层和/或电子阻隔层中包括至少一种上述的螺二芴类有机电致发光化合物。
一种有机电致发光器件，包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，空穴传输层中包括至少一种上述的螺二芴类有机电致发光化合物。
本发明的有益效果：
本发明设计的有机电致发光化合物材料引入叔丁基的螺二芴结构，该结构具有良好的芳香性及热稳定性；同时叔丁基是很好的供电子基团，能够大幅度增加螺二芴的电子云密度，使该类材料具有独特的光电学性质，并且该结构由于其较高的电子云密度使得材料本身的HOMO能级降低，进而降低空穴注入层(HIL)与空穴传输层(HTL)之间势能垒，更有利于空穴的传输，进而有效降低了有机电致发光器件的驱动电压及能耗。叔丁基的引入大大降低了材料的平面性及结晶性，进而大幅度扩展了该类材料的使用范围，能够明显提高有机电致发光器件的制备良率，降低有机电致发光器件的制造成本。
连接对称或非对称的支链结构，大幅度提高了材料分子的扭矩及丰富度控制了材料分子的自由度，直接有效的破坏了分子的平面性及结晶性，避免材料的聚集作用，能有有效提高材料的玻璃化温度。通过调整该材料分子的支链结构能够有效调节并控制该类材料的空穴传输速率，以进一步提高材料的空穴传输性能，进而提高器件的使用寿命及发光效率，例如化合物G69、G74由于支链I及支链II具有很强的扭矩及空间位阻，有效抑制了材料的自由旋转及扭动。
因此经过器件验证，该两款材料均具有很低的驱动电压、良好的寿命及发光效率。
另外，氘(D)即氢(H)的同位素，氘(D)的引入能够相应的增加材料的热稳定性，提高材料的使用寿命，进而提高有机电致发光器件的使用寿命。例如化合物G86,其支链III，相比较上述支链II，由于氘的引入，其器件的寿命有一定的提高。
综上：本发明设计的材料相较对比文件，寿命有极大的提高，效率大幅度提高，驱动电压也有非常大的降低。
具体实施方式
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1：
化合物G20的具体合成方法如下：
(1)将化合物1(0.1mol，25.7g)、FeCl3(0.1eq，0.01mol，1.62g)、CS2(514g，化合物1的20倍质量)加入到反应瓶中，冰浴下加入氯代叔丁烷(1.1eq，0.11mol，10.18g)，加完后缓慢恢复室温反应10h后,反应液倒入冰块(1028g，冰块质量为CS2的2倍质量)中，滴加盐酸至体系pH至2-3，再加入二氯甲烷(1028g，CS2的2倍质量)进行萃取，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物2的粗品，经过柱层析提纯后得到化合物2纯品(18.3g，收率58.3％)，MS(EI)：314(M+)；
(2)氮气保护下将化合物3(1eq，57mmol，16.5g)、无水THF(165g，化合物3的10倍质量)加入到反应瓶中，液氮降温至-78℃，滴加正丁基锂(1.1eq，62.7mmol)，反应30min后，将化合物2(18g，57mmol)、无水THF(180g，化合物2的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入饱和氯化铵溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物4的粗品，经过柱层析提纯后得到化合物4纯品(10.5g，收率31.8％)，MS(EI)：580(M+)；
(3)将化合物4(10g，17mmol)加入到异丙醇(100g，化合物4的10倍质量)中，再滴加盐酸(1M，100g，化合物4的10倍质量)，加热共沸反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物5(9.4g，收率97％)，MS(EI)：562(M+)；
(4)氮气保护下，将化合物5(9g，16mmol)、化合物6(1.1eq,361g/mol,17.6mmol，6.35g)、叔丁醇钠(1.1eq，96.1g/mol,17.6mmol，1.69g)、Pd2(dba)3(5％eq，0.8mmol，0.732g)、三叔丁基膦(5％eq，202.317g/mol，0.8mmol，1.62g)、甲苯(90g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G20(8.43g，收率62.4％)，MS(EI)：843(M+)。
实施例2：
化合物G116的具体合成方法如下：
(1)氮气保护下化合物7(1eq，288g/mol,57mmol，16.4g)、无水THF(164g，化合物7的10倍质量)加入到反应瓶中.液氮降温至-78℃，滴加正丁基锂(1.1eq,62.7mmol)，反应30min后，将化合物1(14.7g，257.97g/mol,57mmol)、无水THF(147g，化合物2的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入氯化铵溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物8的粗品，经过柱层析提纯后得到化合物8纯品(15.2g，收率57.1％)，MS(EI)：468(M+)；
(2)将化合物8(15g，32mmol)加入到异丙醇(150g，化合物8的10倍质量)中，再滴加盐酸(1M，150g，化合物8的10倍质量)，加热至共沸，反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物9(13.8g，收率95.8％)，MS(EI)：450(M+)；
(3)氮气保护下，将化合物9(13.5g，30mmol)、化合物6(1.1eq,361g/mol,33mmol，11.91g)、叔丁醇钠(1.1eq，96.1g/mol,33mmol，3.17g)、Pd2(dba)3(5％eq，915.72g/mol，1.65mmol，1.51g)、三叔丁基膦(5％eq，202.317g/mol，1.65mmol，3.34g)、甲苯(135g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G116(12.6g，收率57.5％)，MS(EI)：731(M+)。
实施例3：
化合物G148的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物10(1.1eq,321g/mol,24.4mmol，7.84g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd2(dba)3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G148(7.63g，收率49.9％)，MS(EI)：691(M+)。
实施例4：
化合物G154的具体合成方法如下：
(1)氮气保护下将化合物3(1eq，344.11g/mol，29mmol，10g)、无水THF(100g，化合物3的10倍质量)加入到反应瓶中，液氮降温至-78℃，滴加正丁基锂(1.1eq，31.9mmol)，反应30min后，将化合物1(9.48g，257.97g/mol，29mmol)、无水THF(94.8g，化合物1的10倍质量)混匀后滴入，-78℃下继续反应2h，然后再加入氯化铵溶液淬灭，缓慢恢复室温后加入二氯甲烷和水萃取分液，二氯甲烷相分出后多次水洗，无水硫酸钠干燥，减压浓缩得到化合物11的粗品，经过柱层析提纯后得到化合物11纯品(8.32g，收率54.7％)，MS(EI)：524(M+)；
(2)将化合物11(8g，15.2mmol)加入到异丙醇(80g，化合物11的10倍质量)中，再滴加盐酸(1M，80g，化合物11的10倍质量)，加热共沸反应5h后减压蒸馏脱异丙醇，抽滤，得到化合物12(7.33g，收率95.3％)，MS(EI)：506(M+)；
(3)氮气保护下，将化合物12(7g，13.8mmol)、化合物13(1.1eq,378.22g/mol,15.2mmol，5.74g)、叔丁醇钠(1.1eq，96.1g/mol,15.2mmol，1.46g)、Pd2(dba)3(5％eq，915.72g/mol，0.69mmol，0.63g)、三叔丁基膦(5％eq，202.317g/mol，0.69mmol，0.139g)、甲苯(70g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G154(4.1g，收率36.9％)，MS(EI)：804(M+)。
实施例5：
化合物G108的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物14(1.1eq,321g/mol,24.4mmol，7.84g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd2(dba)3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G108(8.1g，收率52.9％)，MS(EI)：691(M+)。
实施例6：
化合物G144的具体合成方法如下：
步骤(1)和步骤(2)与实施例2中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物9(10g，22.2mmol)、化合物15(1.1eq,378g/mol,24.4mmol，9.22g)、叔丁醇钠(1.1eq，96.1g/mol,24.4mmol，2.35g)、Pd2(dba)3(5％eq，915.72g/mol，1.11mmol，1.02g)、三叔丁基膦(5％eq，202.317g/mol，1.11mmol，0.223g)、甲苯(100g，化合物9的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G144(6.3g，收率37.9％)，MS(EI)：748(M+)。
实施例7：
化合物G272的具体合成方法如下：
步骤(1)、步骤(2)、步骤(3)与实施例1中操作基本相同，步骤(4)如下：
(4)氮气保护下，将化合物5(10g，17.8mmol)、化合物16(1.1eq,516g/mol,19.6mmol，10.1g)、叔丁醇钠(1.1eq，96.1g/mol,19.6mmol，1.88g)、Pd2(dba)3(5％eq，915.72g/mol，0.89mmol，0.81g)、三叔丁基膦(5％eq，202.317g/mol，0.89mmol，0.18g)、甲苯(100g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G272(7.1g，收率39.9％)，MS(EI)：998(M+)。
实施例8：
化合物G247的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物17(1.1eq,486.21g/mol,21.7mmol，10.54g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G247(9.6g，收率53.3％)，MS(EI)：912(M+)。
实施例9：
化合物G251的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物18(1.1eq,514.24g/mol,21.7mmol，11.16g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G251(9.45g，收率50.8％)，MS(EI)：940(M+)。
实施例10：
化合物G155的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物19(1.1eq,375.2g/mol,21.7mmol，8.14g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G251(7.7g，收率50.8％)，MS(EI)：801(M+)。
实施例11：
化合物G86的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物20(1.1eq,378.2g/mol,21.7mmol，8.21g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G86(13.04g，收率51.9％)，MS(EI)：804(M+)。
实施例12：
化合物G69的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物21(1.1eq,321.15g/mol,21.7mmol，6.97g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G69(7.51g，收率50.8％)，MS(EI)：747(M+)。
实施例13：
化合物G305的具体合成方法如下：
步骤(1)、步骤(2)与实施例4中操作基本相同，步骤(3)如下：
(3)氮气保护下，将化合物12(10g，19.8mmol)、化合物22(1.1eq,321.15g/mol,21.7mmol，6.97g)、叔丁醇钠(1.1eq，96.1g/mol,21.7mmol，2.09g)、Pd2(dba)3(5％eq，915.72g/mol，0.99mmol，0.91g)、三叔丁基膦(5％eq，202.317g/mol，0.99mmol，0.2g)、甲苯(100g，化合物12的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G305(7.46g，收率44.2％)，MS(EI)：852(M+)。
实施例14：
化合物G307的具体合成方法如下：
步骤1-3与实施例1中操作基本相同
(4)
氮气保护下，将化合物5(9g，562.2g/mol16mmol)、化合物23(1.1eq,426.17g/mol,17.6mmol，7.5g)、叔丁醇钠(1.1eq，96.1g/mol,17.6mmol，1.69g)、Pd2(dba)3(5％eq，0.8mmol，0.732g)、三叔丁基膦(5％eq，202.317g/mol，0.8mmol，1.62g)、甲苯(90g，化合物5的10倍质量)加入反应瓶中，加料完毕后升温至回流反应5h，反应完毕后降至室温后加入100ml水进行搅拌15min后过滤得滤液，滤液分液后得有机相，有机相使用无水硫酸镁干燥后旋干经过柱层析提纯后得到高纯度的G307(8.82g，收率60.7)，MS(EI)：908(M+)。
以下将通过实施例和对照例对本发明进行详细的说明。下属实施例于对照例只是为了举例说明本发明，本发明的范围并不限于下述实施例和对照例。
《有机电致发光器件的制造》
应用例1:
其采用ITO作为反射层阳极基板材料，并以N2等离子对其进行表面处理。在阳极基板上方，向空穴注入层(HIL)沉积HAT-CN10纳米厚度的HAT-CN，在其上方选择本发明化合物G1以120纳米厚度形成空穴传输层(HTL)。在上述空穴传输层(HTL)上,真空蒸镀形成blueEML的9,10-Bis(2-naphthyl)anthraces(ADN)作为发光层，形成以2,5,8,11-Tetra-Butyl-Perilene(t-Bu-Perylene)为dopant材料，掺杂约5％的25纳米厚度形成发光层，并在上方以1:1的比例混合蒸镀35纳米厚度的ETM和LiQ到电子输送层(ETL)，之后在电子注入层(EIL)上以2纳米厚度的LiQ进行蒸镀。此后在阴极将镁(Mg)和银(Ag)以9:1的比例混合且以厚度为15纳米进行蒸镀,在上述阴极封口层上沉积65纳米厚度的N4,N4′-BIS[4-BIS(3-methylphenyl)Amino phenyl)]-N4,N4′-Diphenyl-[1,1′-Biphenyl]-4,4′Diamin(DNTPD)。
此外，在阴极表面以UV硬化胶合剂和含有除湿剂的封装薄膜(seal cap)进行密封，以保护有机电致发光器件不被大气中的氧气或水分所影响的同时制造有机电致发光器件。
应用例2-11
分别以化合物G20、G69、G74、G86、G148、G154、G155、G247、G251、G272作为空穴传输层(HTL)物质，其他部分与应用例1一致，据此制作出应用例2～11的有机电致发光器件。
对照例1、2
与应用例1的区别在于，使用对比文件US2017331039A1中的化合物1-13及1-21代替本发明的化合物作为空穴传输层，其余与应用例1相同。
上述应用例制造的有机电致发光器件及对照例制造的有机电致发光器件的特性是在电流密度为10mA/cm2的条件下测定的，结果如表1所示。
表1：
由如上表1的实验对比数据可知，采用本发明所述的化合物制备的有机电致发光器件与对照例相比，电压大幅度降低，发光效率显著提高。由此可见，本发明的化合物能使器件的驱动电压大大降低，大幅度减少了电能的消耗、显著提高了发光效率。另外通过降低驱动电压，有机电致发光器件的寿命有显著提高。
Claims (4)
1.一种螺二芴类有机电致发光化合物，其特征在于，所述螺二芴有机电致发光化合物为下列结构式化合物中的一种：
2.如权利要求1中任一项所述的螺二芴类有机电致发光化合物在制备发光器件中的应用。
3.一种有机电致发光器件，其特征在于，包括阳极、空穴注入层、空穴传输层、电子阻隔层、发光层、空穴阻隔层、电子传输层、电子注入层和阴极，空穴传输层和/或电子阻隔层中包括至少一种如权利要求1中任一项所述的螺二芴类有机电致发光化合物。
4.一种有机电致发光器件，其特征在于，包括阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，空穴传输层中包括至少一种如权利要求1中任一项所述的螺二芴类有机电致发光化合物。
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