CN103038222A - 作为过渡金属络合物的配位体的新型化合物和由其制造的材料，及其应用 - Google Patents
作为过渡金属络合物的配位体的新型化合物和由其制造的材料，及其应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- -1 cationic transition metal Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 230000007812 deficiency Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 125000000623 heterocyclic 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
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- FRBUNLLUASHNDJ-UHFFFAOYSA-N (2-nitrophenyl)hydrazine Chemical compound NNC1=CC=CC=C1[N+]([O-])=O FRBUNLLUASHNDJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001411 amidrazones Chemical class 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- GDAXJBDYNVDMDF-UHFFFAOYSA-N 1,2,4-benzotriazine Chemical compound N1=NC=NC2=CC=CC=C21 GDAXJBDYNVDMDF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000008232 de-aerated water Substances 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002463 imidates Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DGCQHTACQZUATF-UHFFFAOYSA-N 1-[2,6-di(propan-2-yl)phenyl]-2-phenylimidazole Chemical class CC(C)C1=CC=CC(C(C)C)=C1N1C(C=2C=CC=CC=2)=NC=C1 DGCQHTACQZUATF-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ALCSAJMCUCMDLJ-UHFFFAOYSA-N n-methyl-n-[(4-nitrophenyl)diazenyl]aniline Chemical compound C=1C=CC=CC=1N(C)N=NC1=CC=C([N+]([O-])=O)C=C1 ALCSAJMCUCMDLJ-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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Abstract
本发明涉及作为过渡金属络合物的配位体的新型化合物和由此制造的材料，所述材料例如能够作为发射体使用在有机发光电化学池（OLEEC）中。通过本发明首次提出非氟化的缺电子的发射体材料，所述发射体材料能够用在有机发光电化学池中。
Description
技术领域
本发明涉及作为过渡金属络合物的配位体的新型化合物和由其制造的材料，所述材料例如能够作为发射体使用在有机发光电化学池（OLEEC）中。
背景技术
OLEEC在近几年中得到发展并且具有达到有机电子发光二极管（OLED）的功率和与其相比能够更低成本地制造的潜力。
从WO 2010/007107、DE 102009031683和DE 102010005632中已知用于这些器件的作为发射材料的过渡金属络合物。
稳定地发射短波的、也就是发射蓝光的OLEEC发射体仍是特别的难题。这种蓝色的OLEEC发射体迄今为止仅能够以氟化的配位体为基础来获得，其芳香族的基本结构由于氟取代是尤其缺电子的。然而，这种材料在构件中的稳定性仅是极其低的。发射波长在短时间内移动到较长波的光谱范围中，这能够推测出在电场中替换氟。
相反地，没有氟化的配位体系统的OLEEC发射体是使用寿命极其长的，然而不是发射蓝光的。
发明内容
本发明的目的是新型的配位体系统，所述配位体系统在没有氟化的情况下在芳香族的基本结构中具有类似的低的电子密度，进而引起短波的、发蓝光的相同效果。
本发明的主题是3-芳基-苯并-1,2,4-三嗪同系物的缺电子杂环A的新的物质种类，
其中，X代表着-CH=和-N=，并且相邻的苯基环的邻位能够通过化学键彼此连接。
此外，本发明的主题是带有配位体A的阳离子过渡金属络合物的新型的种类，例如配位体A与2-苯基咪唑-配位体结构B或其自身的组合
其中在结构A中，
X代表着-CH=和-N=，并且在结构B中Ar代表着“苯基”或“2,6-二异丙基-1-苯基”，相邻的苯基环的邻位能够通过化学键彼此连接，R1和R2能够彼此无关地为“H”或“苯基”或者共同形成成环的苯环。
最后，本发明的主题是带有配位体A的过渡金属络合物或者将配位体A与配位体B的组合物在有机发光电化学池中的应用。
在下面的反应流程图中，通过Nonoyama合成法来描绘新型的OLEEC发射体的优选的描述。
1.）络合物形成的反应流程图：
近年来，通过Nonoyama法来取得阳离子铱络合物从文献中已知。
所有能够通过纳入配位体A而形成的结构迄今未知。
这种根据本发明的结构C和D是发射蓝光的材料，所述材料为了用在OLEEC设备中必须通过盐置换而设有合适的阴离子。四氟硼酸盐、六氟磷酸盐和六氟锑酸盐是尤其合适的阴离子。离子的液体的阴离子同样是合适的，其有机组分相当于阴离子。
为了形成过渡金属络合物例如使用铱，根据本发明当然也能够将例如为钌、铑、钯、铼、锇、铂、金以及镧系元素用作中心原子。
配位体A的描述出现在反应流程图2之后：
2-硝基苯肼通过与亚氨酸酯的反应转化成氨基腙，所述亚氨酸酯在铂接触部处被氢化并且从催化剂中滤去。将被溶剂释放的还原产物与甲烷硅基化的聚磷酸一起搅拌。
2.）配位体系统A的反应流程图
具体实施方式
N’-（2-硝基苯基）-甲吡啶腙酰胺的描述
将16g（0.104mol；1当量）的2-硝基苯肼和15.55g（0.104mol；1当量）的甲吡啶酰亚胺酸乙酯置于200ml四氢呋喃（THF）中。接着以50℃加热六个小时。在此，在发生反应之后析出深色的沉淀物。薄层色谱分析法的控制（吸附剂：硅胶60；洗脱剂：甲苯/醋酸乙酯4:1）显示出几乎完全的转化。溶剂在旋转式汽化器处被移除，剩余的沉淀物从少量乙醇中重结晶。将其抽出并且用少量冷的乙醇冲洗。
产量：24.2g（90%）；深绿色的、闪亮的粉末
M=257.25g/mol（C12H11N5O2）
熔点：197℃
MS（ESI）：m/z=258.3（[M+H]+）
N’-（2-硝基苯基）-苯并腙酰胺的描述
10g（0.065mol；1当量）的2-硝基苯肼和12.07g（0.065mol；1当量）的安息香酰亚胺酸乙酯-盐酸盐置于220ml由比例为1：1的无水乙醇和四氢呋喃组成的混合物中并且掺入6.58g（0.065mol；1当量）的三乙胺。将其回流煮沸两个小时。在反应混合物冷却之后析出深红色的沉淀物，将所述沉淀物抽出并且用冷的乙醇冲洗。将熔点确定到180℃-182℃。
产量：6.8g（41%）；深红色的、无定形的粉末
M=256.26g/mol（C13H12N4O2）
MS（ESI）：m/z=257.3（[M+H]+）
通过N’-（2-硝基苯基）甲吡啶腙酰胺借助于氢在铂-催化剂处的反应来描述3-（吡啶-2-基）苯并[e][1,2,4]-三嗪
氨基腙的还原在氢化设备中进行：
将8g（0.0311mol）N’-（2-硝基苯基）-甲吡啶腙酰胺在1000ml的锥形瓶中置于500ml的乙醇中。对所述悬浮液提供催化量的铂（IV）氧化物。在将锥形瓶装入到氢化设备中之后，将所需体积的氢导入到设备中并且在有力的搅拌下进行当前的氨基腙的还原。在还原结束之后，将元素的铂滤出并且最大限度地压缩滤液。
对形成的油质的质量进行称重，掺入60ml的三甲基硅多磷酸酯的溶液（如下所描述地来制备）并且回流煮沸一个小时。随后，重新地尽可能地压缩反应物质并且掺入几毫升的水。由此，将缓慢结晶析出的淡黄色的固体从乙醇中重结晶并且随后抽出；在此，留下白色的沉淀物。
产量：1.61g（25%）；白色的、精细粉末状的沉淀物
M=208.22g/mol（C12H8N4）
熔点：145℃
MS（EI）：m/z=208（[M]+）
三甲基硅多磷酸酯的描述：
在带有回流冷却器和干燥管的烧瓶中，将11.37g（0.070mol；1当量）的六甲基二硅氧烷和10g（0.070mol；1当量）的五氧化二磷P2O5在100ml的1,2-二氯乙烷中回流加热大约两个小时，直到所有的P2O5溶解。
B的双-μ-氯代-络合物的描述
在500ml的单颈瓶中，在惰性条件下，将0.69g（2.3mmol；1当量）的铱（III）-氯化物-水合物IrCl13*nH2O和0.40g（6.9mmol；3当量）的氯化钠NaCl置于20ml脱气水中，并且添加溶解在由12ml的脱气水和28ml的2-乙氧基乙醇组成的混合物中的1.76g（4.6mmol；2当量）的1-（2.6-二异丙基苯基）-2-苯基-1H-咪唑。加热到大约50℃，并且在三个小时之后通过直流控制（吸附剂：硅胶60；洗脱剂：甲苯/丙酮9:1）记录到尽可能地转变成络合物。添加200ml的乙醚和20ml的甲醇，抽出产生的黄绿色的固体并且用甲醇冲洗所述固体。化合物能够以32%的产量获得并且在310℃以上分解。
产量：0.54g（32%）；淡黄绿色的沉淀物
M=1669.02g/mol（C84H92C12Ir2N8）
熔点：>310℃（分解）
MS（ESI）：m/z=799.4（[(M/2)-Cl]+）
由A（X=N）和B（双-μ-氯代-络合物）的铱-配位化合物的描述
将0.50g（0.30mmol；1当量）的B（双-μ-氯代-络合物）置于30ml的三氯甲烷中。将0.12g（0.60mmol；2当量）的3-（吡啶-2-基）-苯并[e][1,2,4]-三嗪A（X=N）添加给形成的悬浮液。其回流煮沸大约30分钟。将析出的浅黄色的固体抽出并且用乙醚冲洗。产量为90%。熔点位于194℃，在此材料同时分解。产量：0.56g（90%）；黄色固体，
M=787.29g/mol（C35H25ClIrN7O）
发射最大值（PL）：λmax=484nm（乙腈）。
通过本发明首次提出非氟化的缺电子的发射体材料，所述发射体材料能够使用在有机发光电化学池中。
Claims (5)
1.3-芳基-苯并-1,2,4-三嗪同系物的缺电子的杂环A，
其中
X代表-CH=和-N=，并且相邻的苯基环的邻位能够通过化学键彼此连接。
2.带有根据权利要求1所述的配位体A的阳离子过渡金属络合物，所述配位体A结合2-苯基咪唑-配位体结构B存在或结合其自身存在，
其中在结构A中
X代表-CH=和-N=，并且在结构B中
Ar代表“苯基”或“2,6-二异丙基-1-苯基”，
所述相邻的苯基环的所述邻位（2,2’位）能够通过化学键彼此连接，
R1和R2能够彼此无关地为“氢”或“苯基”或者共同形成成环的苯环并且
中央原子选自铱、钌、铑、钯、铼、锇、铂、金以及镧系元素。
3.用于有机发光电化学池的发光层的材料，所述材料包括带有根据上述权利要求之一所述的配位体A的过渡金属络合物。
4.用于有机发光电化学池的发光层的材料，所述材料包括带有配位体A结合根据权利要求2所述的配位体B的过渡金属络合物。
5.带有配位体A的过渡金属络合物在有机发光电化学池中的应用，或者配位体A与配位体B的组合在有机发光电化学池中的应用。
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| DE102010023959.3 | 2010-06-16 | ||
| PCT/EP2011/058903 WO2011157546A1 (de) | 2010-06-16 | 2011-05-31 | Neue verbindungen als liganden für übergangsmetallkomplexe und daraus hergestellte materialien, sowie verwendung dazu |
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| DE102013225682A1 (de) | 2013-12-12 | 2015-06-18 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Metallionaddukte von neutralen phosphoreszenten Emittern zur Verwendung in lichtemittierenden organischen optoelektronischen Bauteilen |
| CN107722045B (zh) * | 2017-10-31 | 2019-09-24 | 江西理工大学 | 一种对甲基吡啶四氮唑铜[i]配合物蓝光材料及其制备方法 |
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| Title |
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| HANAN AL-AWADI,ET AL.: "Gas-phase thermolysis of condensed-1,2,4-triazines: interesting routes toward heterocyclic ring systems", 《TETRAHEDRON》, vol. 63, 31 December 2007 (2007-12-31), pages 12948 - 12953, XP022350759, DOI: doi:10.1016/j.tet.2007.10.040 * |
| HELMUT GöRNER, ET AL.: "Photoreduction of electron-deficient azaarenes by di- and trialkylamines", 《 J. CHEM. SOC., PERKIN TRANS. 2》, 31 December 2000 (2000-12-31), pages 1723 - 1733 * |
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| DE102010023959A1 (de) | 2011-12-22 |
| US8937175B2 (en) | 2015-01-20 |
| EP2582684A1 (de) | 2013-04-24 |
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