CN1902295A - 基于过芳基化硼烷的发磷光的聚合有机半导体发射极材料,其制备的方法及其应用 - Google Patents
基于过芳基化硼烷的发磷光的聚合有机半导体发射极材料,其制备的方法及其应用 Download PDFInfo
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- CN1902295A CN1902295A CNA2004800394116A CN200480039411A CN1902295A CN 1902295 A CN1902295 A CN 1902295A CN A2004800394116 A CNA2004800394116 A CN A2004800394116A CN 200480039411 A CN200480039411 A CN 200480039411A CN 1902295 A CN1902295 A CN 1902295A
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- Prior art keywords
- arylidene
- phosphorescent
- ligand
- group
- phenyl
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000000463 material Substances 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910000085 borane Inorganic materials 0.000 claims description 26
- 238000007334 copolymerization reaction Methods 0.000 claims description 25
- -1 2,4,6-trimethylphenyl Chemical group 0.000 claims description 24
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 125000002837 carbocyclic group Chemical group 0.000 claims description 3
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
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- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 238000003747 Grignard reaction Methods 0.000 claims description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
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- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
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- 125000000962 organic group Chemical group 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 2
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- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical group NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000027756 respiratory electron transport chain Effects 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
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- 229910052786 argon Inorganic materials 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 6
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- 238000001035 drying Methods 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 5
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- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 5
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- VHHWAUKXFGPSRM-UHFFFAOYSA-N 1-bromo-9h-fluorene Chemical class C12=CC=CC=C2CC2=C1C=CC=C2Br VHHWAUKXFGPSRM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
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- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ODNHQUQWHMGWGT-UHFFFAOYSA-N iridium;oxotin Chemical compound [Ir].[Sn]=O ODNHQUQWHMGWGT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UCDWWJKPBQZZNT-UHFFFAOYSA-N magnesium;oxolane Chemical compound [Mg].C1CCOC1 UCDWWJKPBQZZNT-UHFFFAOYSA-N 0.000 description 1
- CYEBJEDOHLIWNP-UHFFFAOYSA-N methanethioamide Chemical compound NC=S CYEBJEDOHLIWNP-UHFFFAOYSA-N 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 239000010447 natron Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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Abstract
本发明涉及具有半导体性能的发光化合物及其制备方法和其在有机发光二极管(OLEDS)中的应用。还涉及到其中包括中心原子选自过渡金属系统中第8副族的金属络合物的共聚物。
Description
本发明涉及具有半导体性能的发磷光化合物及其制备方法和其在有机发光二极管(OLEDS)中的应用。
在例如出版物M.Kinoshita等的/“Boron containing materials forBlue/blue-violet Electroluminescence”中公开了具有过芳基化硼烷结构的所谓“小分子”(也即是具有适于OLED-应用的发磷光性能的单分子)。
同样也公开了一些特别会发磷光作“小分子”-OLED应用的发光体,例如在M.E.Thompson和S.R.Forrest的出版物和专利中的那些。
小分子的缺点是,它们的适用性很差,因为这些单分子无法通过旋涂或其他涂覆方法制成OLED涂层,而是需要昂贵的施涂方法。
本发明的任务在于提供新型的有机聚合半导体发射极和传送极材料,其可用于有机发光二极管或发光二极管显示器中,且它们易于制得并在物料成型过程中可方便地加工。
本发明内容是发磷光的K型共聚芳基硼烷,
其中:
x,y和z是各成分的摩尔份数并且总和等于1,且其中份数z值为0.01至0.1而x和y的份数之比可在偏离于1的范围内自由选择,
末端连接着氢原子,
M,HT和TE表示共聚物中各个亚芳基成分,
其中的M是基体结构并且具有亚芳基结构,优选是2,7-亚芴基结构,且其在9-位上可方便地被非支链和/或支链的烷基(C1至C10)取代,且其中所述的术语“亚芳基结构”是指任意的二价连接的单环或多环的芳族和/或杂芳族结构,例如在表1中所列的那些(a-x),
并且可通过其他任意排布的一个或多个非支链和/或支链的烷基取代基或者和/或烷氧基取代基R来改善它们在有机溶剂中的溶解性;但或者也可通过烷基取代的亚芳基取代基R1来实现这一点,其中优选使用可简便地与支链或非支链的C5至C10烷基合成的且配置有2,7-二取代的9,9-二烷基亚芴基结构。
HT是具有空穴传递能力的取代2-氨基-噻吩或者-噻唑结构,且具有以下几种可能的变化形式,即
HT(a),取代(2,2’-二氨基-5,5’-二噻吩基)-4,4’-亚基结构,
HT(b),取代二-N,N’-(噻吩-2-基)-或二-N,N’-(1,3-噻唑-2-基)-二氨基亚芳基结构和
HT(c),取代(2,2’-二氨基)-二-(4,4’-噻吩基)-亚芳基-5,5’-亚基结构,并且它们分别可对应于以下所示的通式,
在通式中取代基R2,R3和R4表示又可通过其他任意排布的一种或多种非支链和/或支链的烷基取代基或者和/或烷氧基取代基R取代的芳基Ar,但其中取代基Rn的含义要与相同的指数n一样并且取代基R1的含义也要与亚芳基成分Md的取代基的选择相同;
其中对于HT(b)还有以下条件,即X等于N或者C-R。HT成分用于将空穴传输能力调整到最佳和用于共聚物的更长波发射校正。
TE是二价的发磷光有机金属络合物,具有以下结构:
Me表示第八副族的金属(铱,钌,锇或铂),优选是铱。Ar5是可与金属络合的亚芳基配位体,其同时还带有用于聚合连接的官能团,
配位体(L-X)并不适用于铂络合物,而在所有其他金属络合物中,同样引入可络合的亚芳基配位体(a)、1,3-二酮酸盐配位体(b),二噻唑甲烷-或二噻唑胺-配位体(c)吡啶甲酸盐-(d)、N-芳基水杨醛亚氨基-(e)或8-羟基喹啉盐(-chinolat)-配位体(f),优选是以下结构:
a)单核络合物:
b)双核络合物:
附属的LX配位体有:
Ar是碳环或杂环芳基,其上的氢原子也可任意地被一个或多个支链或非支链的烷基或烷氧基(C1至C10)以及苯基和/或二苯基或萘苯基-氨基基团取代;优选的是2,4,6-三甲苯基、苯基、联苯基、1-萘基、2-萘基、2-二苯基-或2-萘苯基-氨基-3,4-二苯基-噻吩-5-基-和2-二苯基-或2-萘苯基氨基-3,4-二苯基-1,3-噻唑-5-基。
此外,本发明的主题还在于一种根据通用制备方案来制备K型的发磷光共聚芳基硼烷的方法。
反应方案:
该过程中,从溴代的亚芳基成分M、空穴传递成分HT和溴代的发磷光有机金属络合物TE出发,在格林尼亚(Grignard)反应中(参见方案)或者通过锂化作用而进行极性复原(umgepolt)并接着为硼取代,在该反应的产物H中又利用格氏试剂(参见方案)或者相应的锂化试剂用有机基团R来代替硼上的卤素。
最后,本发明的主题还在于K型共聚芳基硼烷在有机发光二极管中作为三重态(triplett)发射层和传输电子的层的用途。
此外,本发明的主题还在于共聚芳基硼烷K作为单组分聚合物的共混物的用途,即针对当比例变量x,y和/或z中的两个为0时的情况。
x,y和z是比例数值,其描述了聚合的各成分彼此是在何种比例下进行的共聚。聚合的各成分也均可作为电致发光层材料使用。
合成方法概述:
从初始合成子A、B和C出发,利用镁四氢呋喃进行格林尼亚反应或者在醚中用BuLi中进行锂化作用。然后单独或以任意所需的比例在THF的沸腾热度下使格林尼亚产物或锂有机基D、E和F与卤化硼G(例如三氟化硼醚合物)反应,并使格林尼亚成分和/或锂有机基的摩尔总数相应于卤化硼的摩尔量。该过程中,二官能基格林尼亚成分在约70℃下只能生成直链的共聚氟代亚芳基硼烷H。
然后,合成另一单官能团的格林尼亚成分I,且在用甲苯(只有在甲苯的沸腾热度下)代替溶剂THF之后按摩尔比例滴加该成分。约120℃下沸腾五小时后,剩余的氟会被格林尼亚成分L的芳基取代并生成发磷光的共聚芳基硼烷衍生物K,且该物质由于其组分比例而具有可裁量的电和光性能。
如果不用格林尼亚化合物I而在干燥冰冷条件下于醚和/或四氢呋喃中合成相应的锂化成分并使其与先前合成得的共聚氟代亚芳基硼烷H反应,则也可得到发磷光的聚芳基硼烷衍生物K。
实施例:
共轭缩合的低聚芳基体系的合成
如果所需的芳基体系不可商购得到,则它们可通过已知的C-C键接反应(例如Suzuki-结合法)而制得,首先即要在至少一个键接单元上进行烷基化或烷氧基化反应,以使得由此形成的聚合材料具有良好的溶解性。
二溴亚芳基M的合成
9,9-二庚基-2,7-二溴代芴的合成
a)9,9-二庚基-芴的合成
在80℃下将0.2mol的芴溶于300ml的DMSO中。向溶液中加入0.01mol的相转移催化剂(Aliquot)并再搅拌5分钟。为烷基化反应需要0.5mol的50%氢氧化钠(Natron lauge)和0.5mol的溴庚烷。添加过程分三步进行,开始时添加三分之一用量的氢氧化钠。溶液自行变为深红色并再添加了溴庚烷之后慢慢变黄。当溶液变黄时,添加第二个三分之一量的氢氧化钠。依此类推。利用乙腈中的RP18的DC来控制反应终点。
用乙醚和水萃取反应混合物三次并分离有机相。在蒸馏除去了所有溶剂(乙醚、DMSO、庚醇)之后,产物以黄色油状形式存在(HPLC-控制),将其作为粗产品进行进一步处理。与此相应地,使用烷基溴化物R-Br(R例如是癸基或2-乙基己基基团)来制备带有不同于庚基的其他烷基的9,9-二烷基芴。
b)2,7-二溴-9,9-二庚基芴的制备
将0.2mol的二庚基芴溶于300ml的氯仿中并加热至沸腾。在黑暗条件下缓慢滴加入0.4mol溶于氯仿中的溴。在沸腾温度下搅拌反应物约12小时。当反应溶液脱色时,结束溴化作用(乙腈中RP18的DC控制)。溶液冷却后蒸馏除去所有的氯仿并且产物以白色晶体形式沉淀于甲醇中。在环己烷中并于硅胶上对产品进行色谱分析之后得到HPLC-纯的产品,mp:45-6℃。
二溴-亚芳基HT的合成/HT(a)结构的构造
1.2-溴代芴的二烷基化作用
在氮气氛中并于约50℃下,在持续搅拌条件下将0.1mol的2-溴代芴溶于DMSO中。向溶解的2-溴代芴中混入0.25mol的叔丁醇钾,反应混合物变成暗红色。5分钟后添加0.25mol的烷基溴化物R-Br;在室温下使反应进行过夜并当颜色由红转变为浅黄时终止反应。
用水洗涤DMSO相并用乙醚萃取。利用旋转蒸发器蒸馏除去醚并且用甲醇沉淀浅黄色晶体形式的产物。
1a)2-溴-9,9-二庚基芴
以这种方式由2-溴代芴和溴庚烷在存在叔丁醇钾的条件下制备例如2-溴-9,9-二庚基芴(mp:32℃)。
2.9,9-二烷基-2-溴代芴的氯乙酰化
将0.1mol的9,9-二庚基-2-溴代芴预先置于二氯甲烷中并用液氮冷却到-15℃。在-15℃下缓慢添加0.15mol的氯乙酰氯并接着加入0.3mol氯化铝。然后搅拌反应物过夜(至少12h)。
将混合物倒入冰/水/HCl(500ml∶500ml∶50ml)中并搅拌20分钟。然后再用水洗涤。分离有机相并蒸去溶剂。产物乙白色晶体形式沉淀于甲醇中。
2a)2-溴-7-氯乙酰基-9,9-二庚基芴
以这种方式由2-溴-9,9-二庚基芴和氯乙酰氯在Friedel-Crafts条件下制备例如2-溴-7-氯乙酰基-9,9-二庚基芴(mp:83-4℃)。
3.芳基化的羧酸酰胺的合成
向一个2 l的带有回流冷却器、磁力搅拌器、滴液漏斗和惰性气体通道的三颈烧瓶中,加入600ml二烷并溶解入1mol二芳基仲胺。然后等当量滴加入各所需的羧酰卤。接着回流加热反应混合物,直至反应中形成的所有量的氢卤化物都被惰性气流去除。通过薄层色谱控制法可另外对反应终点进行监测。然后冷却反应溶液并搅拌到至少两倍量的水中。此时,在多大多数情况下会沉淀析出一种在若干小时后会变硬的油。分离含水相并将粗产品从乙醇中重结晶出。产率各为至少90%。
3a)以这种方式,从苯基-1-萘基-胺和2-苯基乙酰氯制备例如,2-苯基醋酸苯基-1-萘酰胺(熔点:85-88℃)。
3b)以这种方式,从二苯基胺和2-苯基乙酰氯制备例如,2-苯基醋酸-二苯基酰胺(熔点:71-72℃)。
4.芳基化硫代羧酰胺
在回流设备下并利用惰性气体的通入将0.5mol各自芳基化的羧酰胺和等当量Lawesson试剂(由苯甲醚和五硫化磷制得)悬浮分散于750ml的二乙二醇二乙醚中,然后再在100℃下搅拌6h。这过程中会形成一种澄清溶液,在冷却条件下,某些情况下就可从该溶液中结晶出反应产物。为了完全分离产物,将反应混合物搅拌入两倍量的水中,然后使通常形成的油状的相结晶。接着将产物从水相中分离并从甲醇中重结晶出。产率各为至少90%。
4a)以这种方式从2-苯基醋酸苯基-1-萘基酰胺和Lawesson试剂制备例如2-苯基硫代醋酸苯基-1-萘酰胺(熔点:100-103℃)。
4b)以这种方式从2-苯基醋酸-二苯基酰胺和Lawesson试剂制备例如2-苯基硫代醋酸-二苯基酰胺(熔点:142-144℃)。
5.芳基化2-氨基噻吩衍生物的制备
将0.1mol的卤酰基芳基衍生物和0.1mol的2-苯基硫代醋酸二芳基酰胺(实施例4b)预置入四氢呋喃中并在氮气氛下回流30分钟。30分钟后添加0.1mol三甲胺并再回流30分钟。甲醇中沉淀出黄色晶体形式的产物。
5a)2-(苯基-1-萘氨基)-3-苯基-4-对-溴苯基-噻吩
以这种方式从2-苯基硫代醋酸苯基-1-萘酰胺和对-溴苯酰基溴制备例如2-(苯基-1-萘氨基)-3-苯基-4-对溴苯基噻吩(ESI-MS:M+1+=532)。
5b)2-(苯基-1-萘氨基)-3-苯基-4-(7-溴-9,9-二庚基芴-2-基)-噻吩
以这种方式从2-苯基硫代醋酸苯基-1-萘酰胺和2-氯乙酰基-7-溴-9,9-二庚基芴制备例如2-(苯基-1-萘氨基)-3-苯基-4-(7-溴-9,9-二庚基-芴-2-基)-噻吩且R=庚基(ESI-MS:M+1+=816)。
6)通过氧化2-氨基噻吩衍生物制备具有空穴传递性能的二溴亚芳基衍生物
将0.1mol的2-氨基噻吩衍生物和0.5molFeCl3预置入二氯甲烷中并搅拌一天。向产品中混入水和0.1mol的三乙胺并蒸去有机溶剂。产品以黄色结晶形式于残留的水相中沉淀析出。用甲苯在硅胶上通过色谱柱来提纯。
6a)二-[2-(苯基-1-萘氨基)-3-苯基-4-(7-溴-9,9-二庚基芴-2-基)]-5,5’-噻吩基
以这种方式从2-(苯基-1-萘氨基)-3-苯基-4-(7-溴-9,9-二庚基-芴-2-基)-噻吩和氯化铁-III制备例如二-[2-(苯基-1-萘氨基)-3-苯基-4-(7-溴-9,9-二烷基芴-2-基]-5,5’-噻吩基且R=庚基(ESI-MS:M+1+=1629)。
6b)二-[2-(苯基-1-萘氨基)-3-苯基-4-(4-溴苯基)]-5,5’-噻吩基
以这种方式从2-(苯基-1-萘氨基)-3-苯基-4-(4-溴苯基)-噻吩和氯化铁III制备例如二-[2-(苯基-1-萘氨基)-3-苯基-4-(4-溴苯基)]-5,5’-噻吩基(mp:133-4℃),(ESI-MS:M+1+=1061)。
二溴-亚芳基HT的合成/HT(b)结构的构造
1.芳基化二羧酸酰胺的合成
向一个2l的带有回流冷却器、磁力搅拌器、滴液漏斗和惰性气体通道的三颈烧瓶中,加入600ml二烷并溶解入1mol仲的芳基化双胺。然后等当量滴加入各所需的羧酰卤。接着回流加热反应混合物,直至反应中形成的所有量的氢卤化物都被惰性气流去除。通过薄层色谱控制法可另外对反应终点进行监测。然后冷却反应溶液并搅拌到至少两倍量的水中。此时,在多大多数情况下会沉淀析出一种在若干小时后会变硬的油。分离含水相并将粗产品从乙醇中重结晶出。产率各为至少90%。
1a)以这种方式从N,N’-二苯基-对-亚苯基二胺和2-苯乙酰氯制备例如N,N’-二(2-苯乙酰基)-N,N’-二苯基-亚苯基-1,4-二胺(熔点:190℃)。
2.芳基化二硫代羧酸酰胺的合成
在回流设备下并利用惰性气体的通入将0.5mol各自芳基化的二羧酸酰胺和等当量Lawesson试剂(由苯甲醚和五硫化磷制得)悬浮分散于750ml的二乙二醇二乙醚中,然后再在100℃下搅拌6h。这过程中会形成一种澄清溶液,在冷却条件下,某些情况下就可从该溶液中结晶出反应产物。为了完全分离产物,将反应混合物搅拌入两倍量的水中,然后使通常形成的油状的相结晶。接着将产物从水相中分离并从甲醇中重结晶出。产率各为至少90%。
2a)以这种方式从N,N’-二(2-苯乙酰基)-N,N’-二苯基-亚苯基-1,4-二胺和Lawesson试剂制备例如N,N’-二(2-苯基硫代乙酰基)-N,N’-二苯基-亚苯基-1,4-二胺(熔点:224-227℃)。
3.芳基化的二-2-氨基噻吩衍生物的合成
将0.2mol的卤酰基芳基衍生物和0.1mol的N,N’-二(2-苯基硫代乙酰基)-N,N’-二苯基-亚苯基-1,4-二胺预置入四氢呋喃中并在氮气氛下回流30分钟。30分钟后添加0.2mol三甲胺并再回流30分钟。在甲醇中沉淀出浅黄色晶体形式的产物。
3a)以这种方式从N,N’-二(2-苯基硫代乙酰基)-N,N’-二苯基-亚苯基-1,4-二胺和苯酰基溴制备例如N,N’-二苯基-N,N’-二噻吩-3,4-二苯基-2-基-亚苯基-1,4-二胺(熔点:266-268℃)。
二溴-亚芳基HT的合成/HT(c)结构的构造
1.2,2’-二氨基-4,4’-二噻吩基亚芳基的制备
将0.1mol的二-(卤酰基)-亚芳基衍生物和0.2mol的2-芳基-硫代醋酸二芳基酰胺预置入四氢呋喃中并在氮气氛下回流30分钟。30分钟后添加0.2mol三甲胺并再回流30分钟。在甲醇中沉淀出无色晶体形式的产物。
1a)以这种方式从2-苯基-硫代醋酸二苯基酰胺和二-ω-溴乙酰基-对-亚苯基制备例如2,2’-二苯基氨基-3,3’-二苯基-4,4’-二噻吩基-对-亚苯基(熔点:232-235℃)。
二溴-亚芳基-三重态(triplett)发射体-络合物TE的合成
a)配位体的合成:
a1)2-(4-溴苯基)-N,N,N’,N’-四甲基-vinamidinium-高氯酸盐的制备:
在80℃下加热0.1mol的4-溴苯基醋酸和新制的Vilsmeyer-络合物(DMF/POCl3)3h。在于真空中馏去DMF之后将反应混合物加入到含有0.1mol高氯酸钠的冷的水溶液中。抽滤沉淀出的盐并用例如乙醇和乙醚洗涤并吸滤干燥。
白色晶体熔点:145-7℃
a2)3-(4-溴苯基)-h-苯并喹啉的制备
在回流条件下于DMF中加热0.05mol的Vinamidinium盐a1和0.55mol的1-萘基胺,4-5h后冷却并抽吸出沉淀出的晶体淤浆,接着用乙醇和乙醚洗涤。
白色荧光晶体熔点:160℃
a3)5-(4-溴苯基)-2-苯基嘧啶的制备
在回流条件下于吡啶中加热0.05mol的Vinamidinium盐a1和0.055mol的苯甲脒盐酸盐,12h后冷却并馏去吡啶,将反应混合物和甲醇混合。抽吸出析出的晶体,接着用乙醇和乙醚洗涤。
白色荧光晶体熔点:194℃
a4)3-(4-溴苯基)-f,h-二苯并喹啉的制备
在回流条件下于DMF中加热0.05mol的Vinamidinium盐a1和0.055mol的9-氨基-菲,4-5h后冷却并抽吸出析出的晶体淤浆,接着用乙醇和乙醚洗涤。
荧光晶体熔点:℃
b)络合物的合成
1)Ir-二-μ-氯-络合物的一般合成方法:
在回流条件下于100ml甲氧基乙醇和25ml水中加热0.01mol的氯化铱和2.1当量的2-苯基-吡啶-结构成分(例如配位体a2,a3)。12h之后在冷却后将黄色产物抽滤出并用甲醇/乙醚洗涤。
1a)以这种方式得到例如(C^N)2=Ir-μCl2-Ir=(C^N)2型的络合物,且(C^N)=3-(4-溴苯基)-h-苯并喹啉,其产率为65%。
(熔点:>300℃,λmax=462nm THF,ESI-MS=1783.7)
2)(C^N)2=Ir-(LX[b-f])-络合物的一般合成方法:
在30ml的乙氧基乙醇中回流0.005mol的Ir-μ-氯-络合物和2.1当量的阴离子LX-配位体(b-f)和0.005mol的碳酸钠。12h后将产品搅拌入5倍量的甲醇中,抽滤,用甲醇/乙醚洗涤并干燥产物。
2a)以这种方式制得例如(C^N)2=Ir-(LX)型的络合物,且其中(C^N)=3-(4-溴苯基)-h-苯并喹啉并且LX=乙酰丙酮,产品产率为93%
(熔点:>300℃,λmax发射=587nm THF,ESI-MS=956.1)
3)(C^N)2=Ir-(LX[a])-络合物的一般合成方法:
在30ml的甘油中回流0.005mol的(C^N)2=Ir-(acac)-络合物和1.1当量的(a)型LX-配位体。12h后将产品搅拌入5倍量的甲醇中,抽滤,用甲醇/乙醚洗涤并干燥产物。
3a)以这种方式制得例如(C^N)2=Ir-(LX)型络合物,且其中(C^N)=3-(4-溴苯基)-h-苯并喹啉且LX=苯基吡啶,产品产率为74%。
(熔点:>300℃,λmax发射=585nm THF,ESI-MS=1011.2)
格林尼亚化合物D和F的合成
在氩气氛下将0.25mol刚经浸蚀的镁屑预置入干燥的乙醚中。在搅拌和回流条件下滴加溶解于300mlTHF中的0.1mol的高纯度和经干燥的二溴-亚芳基成分M(A)或TE(C),使得反应混合物在反应开始后能保持沸腾。使反应进行过夜。所需的格林尼亚化合物的合成应尽可能同时进行,使得其第二天能够使用。
1a)以这种方式从9,9-二庚基-2,7-二溴代芴和镁制备例如9,9-二庚基-2,7-亚芴基-溴化镁。
1b)以这种方式制得例如一种(C^N)2=Ir-(LX)型的格林尼亚化的络合物,且其中的(C^N)=3-(苯基-4-基-溴化镁)-h-苯并喹啉且LX=苯基吡啶。
另一种替代的锂化化合物D、E和F的合成
在氩气氛下预置入溶于300ml干燥的乙醚/甲苯1∶1中的0.1mol高纯的和经干燥的二溴-亚芳基成分M(A)或TE(C)或未溴化的亚芳基成分HT(B)。在室温搅拌条件下通过隔膜分别注射入等当量的丁基锂。2h后结束所需的锂化化合物的合成过程并将其立即导入到其后的反应中。
1a)以这种方式从9,9-二庚基-2,7-二溴代芴和丁基锂制备例如9,9-二庚基-2,7-亚芴基-锂。
1b)以这种方式从2,2’-二苯基氨基-3,3’-二苯基-4,4’-二噻吩基-对-亚苯基和丁基锂制备例如,2,2’-二苯基氨基-3,3’-二苯基-5,5’-二锂(lithio)-4,4’-二噻吩基-对亚苯基。
1c)以这种方式从N,N’-二苯基-N,N’-二-[(3,4-二苯基)-噻吩-2-基]-亚苯基-1,4-二胺和丁基锂制备例如,N,N’-二苯基-N,N’-二-[(3,4-二苯基-5-基-锂)-噻吩-2-基]-亚苯基-1,4-二胺。
1d)以这种方式制得例如,(C^N)2=Ir-(LX)型的锂化络合物,且其中(C^N)=3-(苯基-4-基-锂)-h-苯并喹啉且LX=苯基吡啶。
直链共聚氟代亚芳基硼烷H的合成
在氩气氛和排除湿气条件下,将溶于THF或乙醚/甲苯1∶1中的所需份数的预制格林尼亚化合物或替代的锂化化合物(D、E和F)转移到其上设置有滴液漏斗、回流冷却器、搅拌器和氩气氛的烧瓶中。在30min的时间内并经由隔膜将对应于金属有机化合物摩尔份数总数的三氟化硼醚化物注入到反应烧瓶中并在60℃下进行搅拌。2h反应时间后,即得到生成的可用于后续反应中去的共聚氟代亚芳基硼烷H。
1a)以这种方式从相应的锂化HT成分和TE成分(上述实施例)和三氟化硼醚合物制得例如含有98%HT成分和2%TE成分的共聚的聚氟代亚芳基硼烷。
格林尼亚化合物I的合成
在氩气氛下将0.15mol刚经浸蚀的镁屑预置入干燥的乙醚中。在搅拌和回流条件下滴加溶解于150mlTHF中的0.1mol的高纯度和经干燥的芳基溴化物,使得反应混合物在反应开始后能保持沸腾。使反应进行过夜。以这种方式合成得到的格林尼亚化合物I应根据共聚氟代亚芳基硼烷H的制备过程进行使用。
1a)以这种方式从2,4,6-三甲苯基溴和镁制得例如2,4,6-三甲苯基-格林尼亚化合物。
另一种替代的锂化化合物I的合成
在氩气氛下预置入溶于50ml干燥的乙醚/甲苯1∶1中的0.01mol高纯的和经干燥的芳基成分I。在室温搅拌条件下通过隔膜注射入等当量的丁基锂。2h后结束所需的锂化化合物的合成过程并将其立即导入到后续反应中。
以这种方式从例如2-二苯基-氨基-3,4-二苯基噻吩和丁基锂制备例如2-二苯基氨基-3,4-二苯基-噻吩-5-基-锂。
发磷光的共聚硼烷K的合成
事先预备装有已制得的共聚氟代亚芳基硼烷H和金属有机化合物I的装置。
首先,用蒸馏桥代替回流冷却器并蒸去溶剂THF。同时用干燥的甲苯填装滴液漏斗至大约等于反应混合物的体积量,并作为溶剂进行滴加以代替THF。在结束了溶剂转换之后,在氩气氛和排除湿气条件下,将所希望的溶解的格林尼亚化合物I或替代的锂化化合物I,按照依据共聚氟代亚芳基硼烷H的化学计量比加料到滴液漏斗中并在甲苯略沸条件下缓慢进行滴加。与此同时蒸去滴加的金属有机化合物I的溶剂(THF或乙醚)。在分离了THF或乙醚之后再将蒸馏桥换成回流冷却器,并在回流条件下再加热5h。冷却后将反应混合物倾倒到冰/HCl上冰分离甲苯相。在旋转蒸发器上将甲苯完全蒸去,然后将残留物溶于少量THF中并在搅拌条件下析出于乙醇中。通过重复溶解于THF和重新析出于乙醇中来进一步提纯产品。
实施例30:
a)以这种方式从共聚氟代亚苯基硼烷H(1a)和2-二苯基氨基-3,4-二苯基-噻吩-5-基-锂I制得例如含铱络合物的发磷光的共聚硼烷K,且其组分比为M∶HT∶TE=0∶49∶1,Tg:85℃,λmax=480nm,GPC:Mw=24500g/mol。
OLED的性能
按照以下的层序列构造OLED:
阳极:ITO(铱-锡氧化物)
120nm Pedot
80nm发射极(根据实施例共聚硼烷Ka)
35nm Alq3
阴极3nm LiF,150nm Al。
a)电流密度
b)功率
该新型材料适于制备可见光谱范围(蓝至红)的不同颜色的电致发光二极管。同样这些材料也可按照相应比例通过共聚反应而转变成可在白色点上或者在其附近区域电致发光的材料。
这些聚合材料可通过所有可由溶液施涂的方法来进行加工(例如旋转涂布、刮涂、筛网印刷、喷墨打印)。
该材料可以高产率制备得到,并且该材料可衍生自结合到芳基化硼烷中的三重态发射的发射体,其中通过选择亚芳基片段(供体/受体结构)而影响电性能并因此影响各化合物的颜色。
特别需要指出的是,为了构造这种聚合物材料不必需其他常规的基于金属-催化的结合反应(因此也就省去了昂贵的分离催化剂的步骤以及消除了骤冷颗粒中由于聚合物的杂质而引起的危险),这就可大大降低合成成本,因为不需要用到昂贵的钯催化剂及其分离步骤。
恰好能发射白光的材料对于光源和其中通过过滤可实现所有颜色的全色显示器的制造是非常有益的。以白光工作的全色显示器的优点是发射极材料不因颜色而老化。
Claims (11)
1.K型发磷光共聚芳基硼烷,
其中:
x,y和z是各成分的摩尔份数并且总和等于1,
末端连接着氢原子,
M,HT和TE表示共聚物中各个亚芳基成分,
其中的M是基体结构并且具有亚芳基结构,且其中所述的术语“亚芳基结构”是指任意的二价连接的单环或多环的芳族和/或杂芳族结构,
HT是具有空穴传递能力的取代2-氨基-噻吩或者-噻唑结构,
TE是二价的发磷光有机金属络合物,具有以下结构:
Me表示第八副族的金属(铱,钌,锇或铂)。
Ar5是可与金属络合的亚芳基配位体,其同时还带有用于聚合连接的官能团,
配位体(L-X)并不适用于铂络合物,而在所有其他金属络合物中L-X表示可络合的亚芳基配位体
和
Ar是碳环或杂环芳基,其上的氢原子也可任意地被一个或多个支链或非支链的烷基或烷氧基(C1至C10)以及苯基和/或二苯基或萘苯基-氨基基团取代。
2.如权利要求1所述的发磷光共聚芳基硼烷,其中份数z值为0.01至0.1而x和y的份数之比可在偏离于1的范围内自由选择。
3.如权利要求1或2之一所述的发磷光共聚芳基硼烷,其中亚芳基结构M优选是2,7-亚芴基结构,其在9-位上可被非支链和/或支链的烷基(C1至C10)取代。
5.如上述权利要求之一所述的发磷光共聚物,其中具有空穴传递能力的取代2-氨基-噻吩或者-噻唑结构HT选自由以下结构HT(a)至HT(c)组成的组,其中
HT(a)是取代(2,2’-二氨基-5,5’-二噻吩基)-4,4’-亚基结构,
HT(b)是取代二-N,N’-(噻吩-2-基)-或二-N,N’-(1,3-噻唑-2-基)-二氨基亚芳基结构和
HT(c)是取代(2,2’-二氨基)-二-(4,4’-噻吩基)-亚芳基-5,5’-亚基结构,并且它们分别可对应于以下所示的通式,
在通式中取代基R2,R3和R4表示又可通过其他任意排布的一种或多种非支链和/或支链的烷基取代基和/或烷氧基取代基R取代的芳基Ar,但其中取代基Rn的含义要与相同的指数n一样并且取代基R1的含义也要与亚芳基成分Md的取代基的选择相同;其中对于HT(b)还有以下条件,即X等于N或者C-R,
6.如上述权利要求之一所述的发磷光共聚物,其中碳环或杂环芳基Ar选自以下化合物组:2,4,6-三甲苯基、苯基、联苯基、1-萘基、2-萘基、2-二苯基-或2-萘苯基-氨基-3,4-二苯基-噻吩-5-基-和2-二苯基-或2-萘苯基氨基-3,4-二苯基-1,3-噻唑-5-基。
7.如上述权利要求之一所述的发磷光共聚物,其中所述的二价发磷光有机金属络合物TE含有铱作为中心原子Me。
10.K型共聚芳基硼烷在有机发光二极管中作为三重态发射层和/或电子传递层用的用途。
11.K型共聚芳基硼烷作为单组分聚合物的共混物的用途,即当比例变量x,y和/或z中的两个为0时。
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2004
- 2004-11-26 TW TW093136553A patent/TWI327590B/zh not_active IP Right Cessation
- 2004-12-29 KR KR1020067015183A patent/KR101249413B1/ko not_active IP Right Cessation
- 2004-12-29 US US10/585,182 patent/US7858724B2/en not_active Expired - Fee Related
- 2004-12-29 DE DE502004008367T patent/DE502004008367D1/de active Active
- 2004-12-29 WO PCT/DE2004/002833 patent/WO2005063919A1/de active Application Filing
- 2004-12-29 CN CNA2004800394116A patent/CN1902295A/zh active Pending
- 2004-12-29 JP JP2006545917A patent/JP5294560B2/ja not_active Expired - Fee Related
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111153822A (zh) * | 2020-01-08 | 2020-05-15 | 北京航空航天大学 | 苯酰基修饰的聚集诱导发光型苯胺齐聚物及其制备方法 |
CN111153822B (zh) * | 2020-01-08 | 2021-07-20 | 北京航空航天大学 | 苯酰基修饰的聚集诱导发光型苯胺齐聚物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1699898A1 (de) | 2006-09-13 |
DE10361385B4 (de) | 2011-07-28 |
US20070191587A1 (en) | 2007-08-16 |
JP2007522271A (ja) | 2007-08-09 |
WO2005063919A1 (de) | 2005-07-14 |
KR20060127101A (ko) | 2006-12-11 |
TW200525010A (en) | 2005-08-01 |
TWI327590B (en) | 2010-07-21 |
DE10361385A1 (de) | 2005-10-13 |
KR101249413B1 (ko) | 2013-04-03 |
EP1699898B1 (de) | 2008-10-29 |
DE502004008367D1 (de) | 2008-12-11 |
JP5294560B2 (ja) | 2013-09-18 |
US7858724B2 (en) | 2010-12-28 |
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