CN113201028B - 基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 - Google Patents
基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN113201028B CN113201028B CN202110562802.1A CN202110562802A CN113201028B CN 113201028 B CN113201028 B CN 113201028B CN 202110562802 A CN202110562802 A CN 202110562802A CN 113201028 B CN113201028 B CN 113201028B
- Authority
- CN
- China
- Prior art keywords
- complex
- iii
- iridium
- methoxy
- phenylquinoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PCXMOGZQVTVBEQ-UHFFFAOYSA-N [Ir+3].C1(=CC=CC=C1)C1=NC2=CC=CC=C2C=C1 Chemical compound [Ir+3].C1(=CC=CC=C1)C1=NC2=CC=CC=C2C=C1 PCXMOGZQVTVBEQ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000010668 complexation reaction Methods 0.000 title description 2
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims abstract description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 5
- MOGTVLAYAVGOJK-UHFFFAOYSA-N 2-[5-(trifluoromethyl)-1h-1,2,4-triazol-3-yl]pyridine Chemical compound FC(F)(F)C1=NNC(C=2N=CC=CC=2)=N1 MOGTVLAYAVGOJK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HDHQZCHIXUUSMK-UHFFFAOYSA-N 4-hydroxy-2-quinolone Chemical compound C1=CC=C2C(O)=CC(=O)NC2=C1 HDHQZCHIXUUSMK-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LVWGQKSYKDQZKF-UHFFFAOYSA-N 2-chloro-4-methoxyquinoline Chemical compound C1=CC=C2C(OC)=CC(Cl)=NC2=C1 LVWGQKSYKDQZKF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 7
- -1 phenylboronic acid compound Chemical class 0.000 claims description 7
- CYRONKIISXPXER-UHFFFAOYSA-N 2,4-dibromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC(Br)=C21 CYRONKIISXPXER-UHFFFAOYSA-N 0.000 claims description 6
- XSZBLRGKCBUWRJ-UHFFFAOYSA-N 2,4-dimethoxyquinoline Chemical compound C1=CC=CC2=NC(OC)=CC(OC)=C21 XSZBLRGKCBUWRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- LJYFMHAOCYPGMX-UHFFFAOYSA-N 4-methoxy-1h-quinolin-2-one Chemical compound C1=CC=C2C(OC)=CC(=O)NC2=C1 LJYFMHAOCYPGMX-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000000295 complement effect Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002346 layers by function Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 238000012360 testing method Methods 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000000295 emission spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical group CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
技术领域
本发明属于有机光电材料技术领域,具体涉及一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物及其制备方法和应用。
背景技术
随着无机半导体电子材料和器件的不断发展成熟,无机材料的电子性能的提高、尺寸的减少以及成本的降低都具有较大的难度。相对于无机半导体材料,有机半导体材料具有易修饰、成本低、柔性及生物相容性好的特点,并且可以很好的实现信息显示、传感、存储和光电转换的功能,在未来的电子器件领域具有无限潜力。
在有机半导体材料中,金属铱(III)配合物因为其发射波长易调节、量子效率高、热化学稳定性高等优势而被认为是优异的电致发光材料,具有良好的应用前景。改变铱(III)配合物环金属主配体的共轭程度、引入推电子和拉电子基团以及引入不同的辅助配体可以改变配合物的HOMO和LUMO轨道能级,能隙大小随之发生变化,可以调节发射波长,从而实现各个不同波段的发光。经过长时间的发展,磷光金属铱(III)配合物已经被广泛应用于有机电致发光全彩显示器件中。而在白光OLEDs领域,磷光金属铱(III)配合物仍有巨大的发展空间,例如黄色磷光金属铱(III)配合物具有高量子效率和宽的发射半峰宽等特点,在互补色白光器件中应用较多,可以制备结构相对简单的蓝光-黄光互补色白光器件。此外,使用宽发射谱带的黄色磷光金属铱(III)配合物也有助于提升白光器件的显色指数。但是,现有技术中还未见新型黄色磷光铱(III)配合物的报道。
发明内容
针对上述技术问题,本发明设计一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物及其制备方法和应用,为进一步开发新型电致发光材料、设计新型黄色磷光铱(III)配合物以及制备白光OLEDs器件提供了思路和方法。
为了实现上述目的,本发明采用以下技术方案:在2-苯基喹啉的苯环的3、4碳位点上引入F、CF3、Cl、Br基团,喹啉的4位碳原子位点上引入给电子性质的甲氧基基团,然后与金属铱、辅助配体配位组合形成新型黄色磷光铱(III)配合物。
本发明公开的一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物,具有如下结构通式:
其中,R1、R2分别为H、F、CF3、Cl、B中的一种;
所述辅助配体A^L为乙酰丙酮、吡啶-2-甲酸、2-[5-(三氟甲基)-1H-1,2,4-三唑-3-基]吡啶中的一种。
本发明还公开上述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,制备路线如下:
所述的一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物具体合成步骤为:
(1)化合物2的制备:将化合物1(2,4-二羟基喹啉)和POBr3放入反应瓶中,所述2,4-二羟基喹啉与POBr3的摩尔比为1:3,在100℃的温度下,反应30分钟,将得到的产物用适量的K2CO3水溶液调节,使溶液偏中性,产物析出,二氯甲烷萃取产物,分液得到有机相,无水Na2CO3干燥,得到化合物2;
(2)化合物3的制备:取化合物2(2,4-二溴喹啉)、CH3ONa,所述2,4-二溴喹啉与CH3ONa的摩尔比为1:5,溶解于超干甲醇中,在无水环境中,反应温度70℃,反应9h,减压旋干后加入CH2Cl2溶解,水洗三次,干燥,得到化合物3;
(3)化合物4的制备:取化合物3(2,4-二甲氧基喹啉)、冰乙酸、浓HCl混合,所述2,4-二甲氧基喹啉、冰乙酸、浓HCl的摩尔比为1:430:320,温度90℃下,反应3.5h,反应后将反应体系冷却至室温,然后将反应液逐渐滴加入适量水中,析出大量絮状沉淀,抽滤,水洗,真空干燥得到化合物4;
(4)化合物5的制备:取化合物4(2-羟基-4-甲氧基喹)、POCl3放入反应瓶中,所述2-羟基-4-甲氧基喹与POCl3的摩尔比为1:3;在85℃的温度下,搅拌反应30分钟,停止反应,将得到的混合物滴加至适量水中,用适量的K2CO3水溶液调节,使溶液偏弱碱性,析出产物,二氯甲烷萃取产物,分液得到有机相,无水Na2CO3干燥,抽滤分离,旋转蒸发溶剂得到化合物5;
(5)化合物7的制备:将化合物5(2-氯-4-甲氧基喹啉)与苯硼酸化合物6以及四(三苯基膦)钯催化剂,加入到甲苯、甲醇、碳酸钾饱和溶液的混合溶剂中,所述2-氯-4-甲氧基喹啉与苯硼酸化合物的摩尔比为10:11,在85℃温度下,氮气保护,回流反应18h,冷却至室温,将有机溶剂旋干,通过柱层析分离技术分离提纯得到化合物7;
(6)化合物8的制备:将化合物7(主配体)和IrCl3·3H2O加入到乙二醇乙醚和去离子水的混合溶剂中,所述化合物7与IrCl3·3H2O的摩尔比为11:5,在氮气保护下,回流反应24h,冷却至室温,加入适量水,大量沉淀析出,抽滤,洗涤,真空干燥得到μ-氯桥二聚体化合物8;
(7)金属铱(III)配合物的制备:将化合物8(μ-氯桥二聚体)、辅助配体以及碳酸钾粉末加入二氯甲烷溶剂中,所述μ-氯桥二聚体化合物与辅助配体的摩尔比为5:11,通过一步简单温和的配位反应,得到目标铱(III)配合物;通过柱层析分离技术可分离提纯出黄色铱(III)配合物,旋转蒸发溶剂得到黄色粉末配合物9。
本发明所述的一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物可用作电致发光材料,制备掺杂型有机电致发光器件。
本发明所述的一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物可用作互补色白光OLED发光材料,制备白光OLED器件。
本发明还公开一种有机电致发光器件,至少一层有机功能层中包含有上述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物。
本发明的原理及有益效果:
本发明的一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物,通过喹啉的4位碳位点上引入给电子性质的甲氧基团以及在苯环中引入F、CF3、Cl、Br基团,引入给电子和吸电子基团以及引入不同的辅助配体,改变配合物的HOMO和LUMO轨道能级,能隙大小随之发生变化,从而调节发射波长,实现配合物的激发态性质的调控。本发明中基于甲氧基取代基的2-苯基喹啉黄光铱(III)配合物具有黄光发射、大的发射半峰宽、高的量子效率等特性,可以用作电致发光材料,应用于有机电致发光器件中,实现黄光OLEDs电致发光;该类黄光配合物具有宽发射谱带可以覆盖更多的白光光谱,有助于提升白光器件的显色指数,可以与蓝光材料共同掺杂实现白光发射。
附图说明
图1:2,4-二甲氧基喹啉氢谱;
图2:2-羟基-4-甲氧基喹啉氢谱;
图3:2-氯-4-甲氧基喹啉氢谱;
图4:2-(4-氟-3-三氟甲基苯基)-4-甲氧基喹啉氢谱;
图5:2-(4-氟-3-三氟甲基苯基)-4-甲氧基喹啉氟谱;
图6:配合物Ir1氢谱;
图7:配合物Ir1氟谱;
图8:配合物Ir2氢谱;
图9:配合物Ir2氟谱;
图10:配合物Ir3氢谱;
图11:配合物Ir3氟谱;
图12:配合物Ir1、Ir3晶体结构图;
图13:金属铱(III)配合物Ir1、Ir2、Ir3紫外-可见吸收光谱和常温发射光谱图;
图14:金属铱(III)配合物Ir1、Ir2、Ir3低温发射光谱;
图15:金属铱(III)配合物Ir1、Ir2、Ir3磷光寿命测试;
图16:金属铱(III)配合物Ir1、Ir2、Ir3电化学曲线。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实例。
以下实施例主要是基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的一种具体结构进行制备方法和性能表征的具体描述。
实施例1:一类基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备
(1)化合物2的制备:将2,4-二羟基喹啉(1mol,1g)和POBr3(3mol,5.33g)放入反应瓶中,在100℃的温度下,反应30分钟,将得到的产物用适量的K2CO3水溶液调节,使溶液偏中性,产物析出,二氯甲烷萃取产物,分液得到有机相,无水Na2CO3干燥,经点板判断所得产物为纯品,产率86%。
(2)化合物3的制备:取2,4-二溴喹啉(1mol,500mg)、CH3ONa(5mol,565mg),超干甲醇25mL,在无水环境中,反应温度70℃,反应9h,减压旋干后加入CH2Cl2溶解,水洗,干燥,抽滤,通过柱层析法提纯,产率85%。1H NMR(400MHz,CDCl3,δ):8.08(d,J=8.0Hz,1H),7.82(d,J=8.5Hz,1H),7.63(m,1H),7.36(m,1H),6.25(s,1H),4.09(s,3H),4.01(s,3H).
(3)化合物4的制备:取200mg的2,4-二甲氧基喹啉、冰乙酸25mL、浓HCl 10mL,温度90℃下,反应3.5h,反应后将反应体系冷却至室温,然后将反应液逐渐滴加入250mL水中,析出大量絮状沉淀,抽滤,水洗,真空干燥得到化合物4,产率90%。1H NMR(400MHz,CDCl3,δ):11.38(s,1H),7.77(d,J=4.0Hz,1H),7.51(t,J=4.0Hz,1H),7.29(d,J=8.0Hz,1H),7.16(t,J=8.2Hz,1H),5.89(s,1H),3.93(s,3H).
(4)化合物5的制备:取2-羟基-4-甲氧基喹啉(1mol,1g)、POCl3(3mol,2.62g),在85℃的温度下,搅拌反应30分钟,停止反应,将得到的混合物滴加至500mL的水中,用适量的K2CO3水溶液调节,使溶液偏弱碱性,析出产物,二氯甲烷萃取产物,分液得到有机相,无水Na2CO3干燥,经点板判断所得产物为纯品,产率86%。1H NMR(400MHz,CDCl3,δ):8.18-8.09(m,1H),7.94(d,J=8.5Hz,1H),7.71(m,1H),7.51(m,1H),6.74(s,1H),4.06(s,3H).
(5)化合物7的制备:将化合物5(1mol,2g)与4-氟-3-三氟甲基苯硼酸化合物6(1.05mol,3.29g)以及四(三苯基膦)钯(0.05mol,0.60g),加入到80mL甲苯、10mL甲醇、10mL碳酸钾饱和溶液的混合溶剂中,在85℃温度下,氮气保护,回流反应20h,冷却至室温,二氯甲烷萃取,并用水洗,无水碳酸钠干燥,抽滤并减压旋干溶剂,再通过色谱柱分离法提纯粗产物,洗脱剂为石油醚:乙酸乙酯100:1来进一步提纯,减压旋干得到白色晶体粉末化合物7,产率82%。1H NMR(400MHz,CDCl3,δ):8.39(dd,J=6.8,2.2Hz,1H),8.35-8.29(m,1H),8.21(d,J=8.3Hz,1H),8.11-8.06(m,1H),7.74(t,J=8.4Hz,1H),7.52(t,J=8.2Hz,1H),7.35(t,J=9.3Hz,1H),7.12(s,1H),4.15(s,3H).19F{1H}NMR(376MHz,CDCl3δ):-61.28(s),-61.31(s),-114.22(s),-114.25(s),-114.29(s),-114.32(s).
(6)化合物8的制备:将化合物7(2.2mmol,597mg)和IrCl3·3H2O(1mmol,300mg)加入到乙二醇乙醚(30mL)和去离子水(10mL)的混合溶剂中,在氮气保护下,110℃回流反应24h,冷却至室温,加入适量水,大量沉淀析出,抽滤,洗涤,真空干燥得到μ-氯桥二聚体化合物4;
(7)金属铱(III)配合物Ir1、Ir2、Ir3的制备:将环金属铱(III)氯桥二聚体(1mmol,100mg)分别与辅助配体2.2mol(Ir1:乙酰丙酮12.3mg;Ir2:吡啶-2-甲酸15.73mg;Ir3:2-[5-(三氟甲基)-1H-1,2,4-三唑-3-基]吡啶27.1mg)以及碳酸钾粉末(5mmol,43.68mg)加入二氯甲烷溶剂(40mL)中,在N2氛围中25℃搅拌反应12h。反应结束后,将无水碳酸钾粉末抽滤滤除,减压旋蒸旋干溶剂。通过柱层析分离提纯铱(III)配合物Ir1、Ir2、Ir3,洗脱剂比例为石油醚:乙酸乙酯=50:1,产率分别为67%、75%、73%。
Ir1(67%):1H NMR(400MHz,CD2Cl2,δ):8.26(t,J=8.3Hz,4H),8.01(d,J=7.0Hz,2H),7.63-7.46(m,4H),7.42(s,2H),6.31(d,J=11.7Hz,2H),4.77(s,1H),4.32(s,6H),1.56(s,6H).19F{1H}NMR(376MHz,CD2Cl2δ):-60.85(s),-60.88(s),-116.19(s),-116.22(s),-116.26(s),-116.29(s).
Ir2(75%):1H NMR(400MHz,CD2Cl2,δ):8.59(d,J=8.8Hz,1H),8.23-8.10(m,3H),8.05(d,J=6.9Hz,1H),7.94(d,J=5.1Hz,1H),7.72(m,2H),7.57(t,J=7.9Hz,1H),7.47(dd,J=12.4,5.2Hz,3H),7.35(dd,J=10.2,5.0Hz,2H),7.12(d,J=8.8Hz,1H),6.98(dd,J=11.4,4.3Hz,1H),6.68(d,J=11.5Hz,1H),6.12(d,J=11.3Hz,1H),4.32(s,3H),4.29(s,3H).19F{1H}NMR(376MHz,CD2Cl2δ):-60.93(s),-60.97(s),-60.99(s),-61.03(s),-114.60(s),-114.63(s),-114.66(s),-114.69(s),-115.25(s),-115.28(s),-115.31(s),-115.34(s).
Ir3(73%):1H NMR(400MHz,CD2Cl2,δ):8.19(d,J=6.8Hz,1H),8.11(t,J=7.9Hz,2H),8.05(d,J=8.4Hz,1H),7.96(d,J=5.6Hz,1H),7.80(d,J=7.6Hz,1H),7.73(t,J=7.6Hz,1H),7.64(d,J=8.9Hz,1H),7.44(d,J=9.4Hz,2H),7.38-7.29(m,2H),7.25-7.12(m,3H),6.96(dd,J=11.4,4.3Hz,1H),6.57(d,J=11.2Hz,1H),6.33(d,J=11.4Hz,1H),4.27(d,J=1.5Hz,6H).19F{1H}NMR(376MHz,CD2Cl2δ):-60.87(s),-60.90(s),-60.99(s),-61.02(s),-63.73(s),-114.25(s),-114.28(s),-114.31(s),-114.35(s),-114.88(s),-114.91(s),-114.94(s),-114.97(s).
实施例2:金属铱(III)配合物的晶体结构测定
X-射线衍射数据通过Bruker Smart CCD Apex DUO衍射仪收集,通过直接法进行结构解析,并用Olex2软件的全矩阵最小二乘法进行进一步精修。所有计算和分子结构图均用Olex2软件包和Mercury语言来开展进行,晶体结构如图12所示。
实施例3:金属铱(III)配合物紫外-可见吸收光谱测试
吸收光谱测试溶剂为重蒸二氯甲烷溶剂,测试过程无需除氧,分别配制浓度为1x10-5 M的三种配合物的二氯甲烷溶液,先进行空白样的测试,即取两个比色皿均加入2mL的纯二氯甲烷溶液,扫描基线进行空白样测试;之后取出其中用来样品测试的比色皿加入2mL待测样品溶液,进行紫外-可见吸收光谱测试。吸收光谱如图13。
实施例4:金属铱(III)配合物常温发射光谱测试
常温发射光谱测试溶剂为重蒸二氯甲烷溶剂,测试过程无需除氧,分别配制浓度为1x10-5M的三种配合物的二氯甲烷溶液,所有配合物的激发波长均为365nm。如图13所示,Ir1、Ir2、Ir3的常温发射波长分别为:556nm;555nm、528nm;555nm、529nm。Ir1、Ir2、Ir3的常温发射半峰宽为:105nm;106nm;99nm。
实施例5:金属铱(III)配合物低温发射光谱测试
低温发射光谱测试溶剂为2-甲基四氢呋喃,光谱测试浓度为1x10-5 M,发射光谱样品无需除氧,在77K的低温下进行测试,所有配合物的激发波长均为365nm。低温发射光谱如图14所示,Ir1、Ir2、Ir3的低温发射波长分别为:532nm、571nm;515nm、555nm;514nm、552nm。
实施例6:金属铱(III)配合物磷光寿命测试
测试磷光金属铱(III)配合物激发态寿命时需要严格除氧,因为氧气分子的存在会导致激发态猝灭,寿命减少。激发态寿命测试溶剂为重蒸二氯甲烷,测试浓度为1x10-5M,所有配合物的激发波长均为365nm。激发态寿命如图15所示,Ir1、Ir2、Ir3的寿命分别为:0.36μs、1.05μs、1.21μs。
实施例7:金属铱(III)配合物溶液光致发光量子效率测试
通过绝对法使用积分球测试配合物的溶液量子效率,测试溶剂为重蒸二氯甲烷,测试浓度为1x10-5 M,发射光谱样品需充分鼓氮气除氧。Ir1、Ir2、Ir3的溶液量子效率分别为:83.96%、87.15%、55.39%。
实施例8:金属铱(III)配合物电化学测试
电化学测试以四丁基六氟膦酸铵为电解质,玻碳电极为工作电极,铂丝电极为对电极,Ag/AgNO3为参比电极,二茂铁为外标,重蒸二氯甲烷为溶剂,测试浓度为1x10-3 M。Ir1、Ir2、Ir3的电化学曲线如图16所示。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变形,这些改进和变形也应视为本发明的保护范围。
Claims (10)
3.根据权利要求2所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,其特征在于,包括:
将2,4-二羟基喹啉与POBr3反应得到2,4-二溴喹啉;2,4-二溴喹啉与CH3ONa反应生成2,4-二甲氧基喹啉;2,4-二甲氧基喹啉在冰乙酸与浓HCl的作用下生成2-羟基-4-甲氧基喹,然后与POCl3反应得到2-氯-4-甲氧基喹啉;
将2-氯-4-甲氧基喹啉与苯硼酸化合物通过铃木反应得到主配体;
主配体与IrCl3·3H2O反应,得到μ-氯桥二聚体化合物,然后与辅助配体通过配位反应,得到基于甲氧基取代基的2-苯基喹啉黄光铱(III)配合物。
4.根据权利要求3所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,其特征在于,所述2,4-二羟基喹啉与POBr3的摩尔比为1:3,在100℃的温度下,反应30分钟;所述2,4-二溴喹啉与CH3ONa的摩尔比为1:5,溶解于超干甲醇中,在无水环境中,反应温度70℃,反应9h;所述2,4-二甲氧基喹啉、冰乙酸、浓HCl的摩尔比为1:430:320,在温度90℃下,反应3.5h。
5.根据权利要求3所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,其特征在于,所述2-羟基-4-甲氧基喹与POCl3的摩尔比为1:3,在85℃的温度下,搅拌反应30分钟。
6.根据权利要求3所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,其特征在于,所述2-氯-4-甲氧基喹啉与苯硼酸化合物的摩尔比为10:11,将2-氯-4-甲氧基喹啉与苯硼酸化合物以及四(三苯基膦)钯催化剂,加入到甲苯、甲醇、碳酸钾饱和溶液的混合溶剂中,在85℃温度下,氮气保护,回流反应18h。
7.根据权利要求3所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的制备方法,其特征在于,所述主配体与IrCl3·3H2O的摩尔比为11:5,将主配体和IrCl3·3H2O加入到乙二醇乙醚和去离子水的混合溶剂中,在氮气保护下,回流反应24h;所述μ-氯桥二聚体化合物与辅助配体的摩尔比为5:11。
8.根据权利要求1所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的应用,其特征在于,用作电致发光材料,制备电致发光器件。
9.根据权利要求1所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物的应用,其特征在于,用作互补色白光OLED发光材料,制备白光OLED器件。
10.一种有机电致发光器件,其特征在于,至少一层有机功能层中包含有权利要求1所述的基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(III)配合物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110562802.1A CN113201028B (zh) | 2021-05-24 | 2021-05-24 | 基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110562802.1A CN113201028B (zh) | 2021-05-24 | 2021-05-24 | 基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113201028A CN113201028A (zh) | 2021-08-03 |
CN113201028B true CN113201028B (zh) | 2022-12-09 |
Family
ID=77022870
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110562802.1A Active CN113201028B (zh) | 2021-05-24 | 2021-05-24 | 基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113201028B (zh) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100966885B1 (ko) * | 2008-02-29 | 2010-06-30 | 다우어드밴스드디스플레이머티리얼 유한회사 | 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고있는 유기 전계 발광 소자 |
KR20100047466A (ko) * | 2008-10-29 | 2010-05-10 | 다우어드밴스드디스플레이머티리얼 유한회사 | 신규한 전자재료용 화합물 및 이를 포함하는 유기 전자 소자 |
JP4474493B1 (ja) * | 2009-07-31 | 2010-06-02 | 富士フイルム株式会社 | 有機電界発光素子 |
CN102703059A (zh) * | 2012-05-31 | 2012-10-03 | 吉林奥来德光电材料股份有限公司 | 有机磷光发光材料及其制备方法和应用 |
CN103254243A (zh) * | 2013-05-02 | 2013-08-21 | 太原理工大学 | 一种多取代苯基喹啉铱(iii)配合物及其制备方法和应用 |
-
2021
- 2021-05-24 CN CN202110562802.1A patent/CN113201028B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN113201028A (zh) | 2021-08-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kwon et al. | Functionalized phenylimidazole-based facial-homoleptic iridium (III) complexes and their excellent performance in blue phosphorescent organic light-emitting diodes | |
Wong et al. | Multi-functional bis (alkynyl) gold (iii) N⁁ C complexes with distinct mechanochromic luminescence and electroluminescence properties | |
CN109593106A (zh) | 金属配合物、有机电致发光材料、有机电致发光器件 | |
WO2014000581A1 (zh) | 联吡啶三唑类稀土配合物及其制备方法 | |
Yu et al. | Triphenylamine-functionalized iridium (III) complexes for near-infrared phosphorescent organic light emitting diodes | |
CN107434787A (zh) | 一种苯并咪唑高氯酸盐的制备、结构及荧光性质 | |
CN110283216A (zh) | 一种三氘代铱配合物及其制备方法和应用 | |
CN111875634A (zh) | 一种基于苯并咪唑类双齿配体的发光铜化合物及其制备方法 | |
CN107602574A (zh) | 一种以氰基苯为核心的化合物及其应用 | |
CN111848676B (zh) | 一种基于苯并咪唑双膦配体的发光铜化合物及其制备方法 | |
CN104370968B (zh) | 异喹啉金属配合物及其制备方法与应用 | |
WO2016102413A1 (en) | Process for the manufacture of spirodibenzosuberane compounds | |
CN113201028B (zh) | 基于甲氧基调控的宽谱带黄色磷光2-苯基喹啉铱(iii)配合物及其制备方法和应用 | |
CN108047278B (zh) | 一类d-a-d型六元环金属铂(ii)配合物近红外发光材料 | |
Zhang et al. | The effects of substituted picolinate ligands on the photophysical and electrochemiluminescence properties of bis-cylcometalated iridium (III) complexes | |
Xu et al. | The effects of different solvents and excitation wavelength on the photophysical properties of two novel Ir (III) complexes based on phenylcinnoline ligand | |
CN113292607B (zh) | 基于苯并咪唑膦配体的离子型发光铂配合物及其制备方法 | |
CN115010763A (zh) | 一种圆偏振磷光铂(ii)配合物及其制备方法与应用 | |
CN113201022A (zh) | 具有异构体的小共轭磷光金属铱(iii)配合物及其制备方法和应用 | |
Bhagwan et al. | Synthesis, characterization and photoluminescent studies of zinc complexes with heterocyclic ligands comprising N, O donor atoms | |
Li et al. | Synthesis and properties of a novel ruthenium complex containing a 2-(benzimidazol-2-yl)-8-octyloxyquinoline tridentate ligand | |
CN104447874A (zh) | 金属配合物的制备及其应用方法 | |
CN112538097B (zh) | 金属有机配合物及其制备方法和应用 | |
CN111892628B (zh) | 一种基于吡啶并咪唑双膦衍生物的发光铜(i)配合物及其制备方法 | |
CN112940045B (zh) | 一种二价铂络合物及其制备方法和其在发光材料方面的应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |