CN108148079B - 一种膦杂环氯化金(i)配合物、合成方法及其应用 - Google Patents
一种膦杂环氯化金(i)配合物、合成方法及其应用 Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 18
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 title claims abstract description 17
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 15
- 229910003771 Gold(I) chloride Inorganic materials 0.000 title claims description 7
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 5
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
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- HPHZVOOLJMXCIA-UHFFFAOYSA-K thiolane;trichlorogold Chemical compound [Cl-].[Cl-].[Cl-].[Au+3].C1CCSC1 HPHZVOOLJMXCIA-UHFFFAOYSA-K 0.000 claims description 2
- 239000005922 Phosphane Substances 0.000 claims 1
- 229910000064 phosphane Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 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 3
- 230000005540 biological transmission Effects 0.000 description 3
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- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- MWEKPLLMFXIZOC-UHFFFAOYSA-N pyren-1-ylboronic acid Chemical compound C1=C2C(B(O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 MWEKPLLMFXIZOC-UHFFFAOYSA-N 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- UCGCVRKULHHWGA-UHFFFAOYSA-M gold(1+);thiolane;chloride Chemical compound [Au]Cl.C1CCSC1 UCGCVRKULHHWGA-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 pyrene compound Chemical class 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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Abstract
本发明公开了一种膦杂环氯化金(I)配合物、合成方法及其应用,属于有机电致发光材料领域。该类化合物具有式I所示的结构式。本发明有机电致发光化合物可以应用于有机电致发光器件的发光层。该类化合物热稳定性好,膦杂环戊二烯结构的存在有效的减弱了分子间的π‑π堆积作用,膦原子与氯化金(I)配位后可以有效提高相应有机电致发光器件的效率。I。
Description
技术领域
本发明涉及有机电致发光材料领域,具体涉及一种膦杂环氯化金(I)配合物、合成方法及其应用。
背景技术
有机电致发光器件作为一种新型的显示技术,具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点,可以应用在平板显示器和新一代照明上,也可以作为LCD的背光源。自从20世纪80年代底发明以来,有机电致发光器件已经在产业上有所应用,比如作为相机和手机等屏幕。但是目前应用于有机电致发光器件的有机材料仍存在一些问题:热稳定性不高,较低的电子注入和传输能力造成载流子传输不平衡,以及聚集荧光淬灭效应使得在固态薄膜状态时发光效率较低等,这些都是制约有机电致发光器件发展的瓶颈,造成OLED器件效率低,使用寿命短,严重制约其更广泛的应用,特别是大屏幕显示器,因此,为了有机电致发光材料更广泛的应用,需要开发稳定高效的新型材料。
在有机π共轭体系中引入膦原子是一种有效调节材料光电性能的手段。膦原子的引入既可以通过其d轨道与π-共轭体系间的σ-π相互作用来改变材料的电子结构,又具有很好的可修饰性,如被氧化、硫化或与金属配位等,从而能有效地调控材料的光电性能。因此,膦原子的引入为有机光电功能材料的分子结构设计和光电性能改善等方面的研究提供了广阔的空间。膦原子与氯化金(I)配位后可以有效提高相应有机电致发光器件的效率(J.Am.Chem.Soc.,2003,125:9254-9255)。
芘类化合物具有较大的共轭平面,这种刚性结构使得制得的材料拥有高载流子迁移率和空穴注入能力。设计合成含有芘结构的膦杂环氯化金(I)配合物,有望为有机电致发光材料研究开发注入新的活力。
发明内容
根据目前的技术现状,本发明目的在于提供一类热稳定性好、发光效率高的膦杂环氯化金(I)配合物;另一目的在于提供其制备方法和应用。
为实现本发明目的,本发明将膦杂环与芘基团引入同一π-共轭体系,以提高相应有机电致发光器件的效率。
本发明所述的膦杂环氯化金(I)配合物,其结构式为:
所述的膦杂环氯化金(I)配合物的合成方法包括如下步骤:
(a)在氩气保护下,向烧瓶中依次加入1-芘硼酸,邻溴碘苯,四氢呋喃,水,四(三苯基膦)钯,碳酸钾,加热回流反应,反应液后处理得中间体Ⅱ;
(b)在氩气保护下,向烧瓶中加入化合物Ⅱ,四氢呋喃,然后将体系冷却到-60~-80℃,向体系中滴加含正丁基锂的正己烷溶液,滴加完毕后在-60~-80℃反应,将二苯基氯化膦滴加到上述体系,缓慢恢复到室温,反应液后处理得中间体Ⅲ;
(c)向烧瓶中加入化合物Ⅲ,甲苯,醋酸钯,加热回流反应;反应结束后用硅藻土过滤,减压蒸馏除去溶剂,然后向体系中加入二氯甲烷以及四氢噻吩氯化金(I)反应,后处理得化合物Ⅰ。
反应物摩尔比:1-芘硼酸:邻溴碘苯:四(三苯基膦)钯=1:1-1.2:0.001-0.01;化合物Ⅱ:正丁基锂:二苯基氯化膦=1:1-1.2:1-1.2;化合物Ⅲ:醋酸钯:四氢噻吩氯化金(I)=1:0.01-0.1:1-1.2。
所述的膦杂环氯化金(I)配合物的应用,其可用于制备有机电致发光器件。该有机电致发光器件为层状结构,该层状结构设置依次为阳极基板、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层以及阴极金属层;将本发明所述膦杂环氯化金(I)配合物I作为发光层材料。
与现有技术相比,本发明所述的膦杂环氯化金(I)配合物的优点是:
(1)本发明将膦杂环与芘基团引入同一π-共轭体系,既提高了电子传输和注入能力,又可以有效的保证发光层的聚集淬灭效应;膦杂环戊二烯结构的存在有效降低了分子间的堆积效应;另外,膦杂环戊二烯与氯化金(I)配位后可以显著提高相应有机电致发光器件的效率。
(2)本发明结构I所示有机电致发光化合物热稳定性好,以该化合物作为发光层的发光器件具有寿命长等优点。
附图说明
图1为本发明化合物I的热重分析图;
在图中可以看出,化合物I明显失重温度都在400℃以上,说明该类化合物具有较好的热稳定性;
图2为有机电致发光器件结构示意图。
具体实施方式
为了更详细叙述本发明,特举以下例子,但是不限于此。
实施例1化合物Ⅰ的合成
化合物Ⅱ的合成
在氩气保护下,向烧瓶中依次加入1-芘硼酸(24.6g),邻溴碘苯(31.0g),甲苯(300mL),水(30mL),四(三苯基膦)钯(200mg),碳酸钾(27.6g),加热回流反应10h。停止反应,用乙酸乙酯萃取三次,合并有机相,再水洗至中性;分出有机相,加无水硫酸镁干燥,抽滤,旋干;硅胶柱层析得白色固体化合物Ⅱ30.3g,产率85%。
化合物Ⅲ的合成
在氩气保护下,向烧瓶中加入化合物Ⅱ(20g),四氢呋喃(200mL),然后将体系冷却到-78℃,向体系中滴加2.5M的含正丁基锂的正己烷溶液(25mL),滴加完毕后在-78℃反应1小时,将二苯基氯化膦(13.6g)滴加到上述体系,缓慢恢复到室温,加入水(100mL)淬灭反应,用乙酸乙酯萃取三次,合并有机相,再水洗至中性;分出有机相,加无水硫酸镁干燥,抽滤,旋干;硅胶柱层析得白色固体化合物Ⅲ19.5g,产率75%。
化合物Ⅰ的合成
向烧瓶中加入化合物Ⅲ(5.0g),甲苯(100mL),醋酸钯(120mg),加热回流反应10小时。恢复室温后氩气保护下过硅藻土,减压蒸馏除去甲苯,然后向体系中加入二氯甲烷(50mL),然后加入四氢噻吩氯化金(I)(3.8g),室温下反应5小时,加水淬灭反应,分出有机相,加无水硫酸镁干燥,抽滤,旋干;硅胶柱层析得淡黄色固体化合物Ⅰ5.1g,产率76%。
31PNMR(162Hz,CDCl3),δ:-6;1HNMR(400MHz,CDCl3),δ:6.67~6.89(m,5H),7.02~7.78(m,10H),7.83~8.01(m,2H);
ESI,m/z:[M+H]+calcd for C28H18AuClP,理论值:617.0500;实测值:617.0502。
下面是本发明化合物的应用
应用例1:
应用本发明化合物I作为OLED器件中的发光材料,另外选用DPVBi作为本发明对比材料,实施的通用器件结构如下:
ITO/CuPc(10nm)/NPB(50nm)/发光材料(15nm)/Alq3(10nm)/LiF(1nm)/Al(100nm)
所用一些材料的结构式如下:
器件的制备过程如下:首先,将透明导电ITO玻璃基板(上面带有阳极)(中国南玻集团股份有限公司)依次经去离子水,乙醇,丙酮,去离子水洗净,再用氧等离子处理60秒。
然后,真空蒸镀CuPc,形成10nm厚的空穴注入层。
然后,蒸镀NPB,形成50nm厚的空穴传输层。
然后,在空穴传输层上蒸镀15nm厚的发光层。
然后,在发光层上蒸镀10nm厚的Alq3作为电子传输层。
最后,蒸镀1nm LiF为电子注入层和100nm Al作为器件阴极。
所制备的器件用Photo Research PR650光谱仪测试,其器件的光电性能见下表:
从上表可以看出,在相同的条件下,基于本发明化合物I的有机电致发光器件的效率明显高于DPVBi。因此可以看出,本发明化合物制备的有机电致发光器件具有高的效率。
Claims (3)
1.一种膦杂环氯化金(I)配合物,其特征在于,其为具有如下结构式I的化合物:
2.合成如权利要求1所述的膦杂环氯化金(I)配合物的方法,其特征在于,通过如下步骤实现:
(a)在氩气保护下,向烧瓶中依次加入1-芘硼酸,邻溴碘苯,四氢呋喃,水,四(三苯基膦)钯,碳酸钾,加热回流反应,反应液后处理得中间体Ⅱ;
(b)在氩气保护下,向烧瓶中加入化合物Ⅱ,四氢呋喃,然后将体系冷却到-60~-80℃,向体系中滴加含正丁基锂的正己烷溶液,滴加完毕后在-60~-80℃反应,将二苯基氯化膦滴加到上述体系,缓慢恢复到室温,反应液后处理得中间体Ⅲ;
(c)向烧瓶中加入化合物Ⅲ,甲苯,醋酸钯,加热回流反应;反应结束后,硅藻土过滤,减压蒸馏除去溶剂,然后向体系中加入二氯甲烷以及四氢噻吩氯化金(I),反应,反应结束经后处理得化合物Ⅰ。
3.如权利要求1所述的膦杂环氯化金(I)配合物的应用,其特征在于,将其应用于制备有机电致发光器件的发光层材料。
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