CN111925391A - 含三苯基(氧)膦的有机长余辉材料及制备方法和使用方法 - Google Patents
含三苯基(氧)膦的有机长余辉材料及制备方法和使用方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 70
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 9
- 238000012984 biological imaging Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- -1 boric acid ester Chemical class 0.000 claims description 4
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- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
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- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 238000007239 Wittig reaction Methods 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 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 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 16
- 239000012467 final product Substances 0.000 abstract description 6
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- 238000000746 purification Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
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- 229920000642 polymer Polymers 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- YLEYOJVMEWFBHX-UHFFFAOYSA-N N,N-diphenyl-2-phosphanylaniline Chemical compound PC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 YLEYOJVMEWFBHX-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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Abstract
本发明涉及一种含有三苯基(氧)膦的有机长余辉材料,分子结构为TP(O)‑R;其中,TP(O)为三苯基(氧)膦基团,R为芳香环或芳香杂环化合物,TP(O)和R基团通过临位相接,所合成的发光材料拥有螺旋形的分子构型,在大位阻构型和强分子内作用下有效地抑制非辐射跃迁,实现长余辉发光,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。本发明的合成方法工艺简单,容易纯化,所合成的发光材料拥有螺旋形的分子构型,在大位阻构型和强分子内作用下有效地抑制非辐射跃迁,实现长余辉发光,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。有机长余辉材料应用于有机光电、生物成像和防伪等领域。
Description
技术领域
本发明属于有机长余辉材料技术领域,涉及一种含三苯基(氧)膦的有机长余辉材料及制备方法和使用方法,及其作为发光材料在有机电致发光器件、生物成像和防伪等领域的应用。
背景技术
长余辉发光是指在撤去激发光源后仍能维持发光数秒以上(当发光的持续时间超过0.1s,亮度超过0.32mcd/m2,就能很好地通过裸眼分辨和识别,见文献:Xu S,Chen R,Zheng C,Huang W.Excited State Modulation for Organic Afterglow:Materials andApplications.Adv.Mater.,2016,28(45):9920-9940.)的一种光致发光现象,又称为持续发光。长余辉发光是一种理想的信号光源,可以有效地消除常见的短寿命背景光造成的影响,从而大大提高信噪比。具有长余辉发光性能的材料也被称为夜光材料或蓄光型发光材料,这类材料在光学记录、紧急照明、交通标识、防伪、生物成像及光动力治疗等领域具有广阔的应用前景。
长余辉发光材料根据其构成可分为无机长余辉发光材料和有机长余辉发光材料两大类。其中,无机长余辉发光材料经过大量的研究已经能够实现材料发光强、稳定且持续发光时间长等良好性能,可满足商业化的要求。但是,无机长余辉发光材料不仅需要用到贵金属元素,还存在制备能耗高、工艺繁杂、透明度低等问题,难以满足广阔的市场需求和可持续发展的需要。相比之下,有机长余辉发光材料具有分子设计性强、合成容易、价格低廉、分散性佳以及生物相容性好等优点,具有更广阔的应用空间和市场前景,引起了学术界和产业界的广泛关注和研究。
由于有机长余辉材料的研发起步较晚,其种类仍然十分有限,因此,设计合成高效的有机长余辉材料仍是光电材料领域的挑战之一。目前,室温长余辉发光可以通过以下3种方法实现:(1)使用聚合物或小分子化合物为基质,掺杂磷光分子的主客体掺杂体系;(2)利用发光分子修饰聚合物,通过聚合物自身的水氧阻隔性能实现余辉的单一聚合物体系;(3)直接利用小分子自身晶体阻隔水氧的纯有机小分子晶体体系。其中,纯有机小分子晶体是目前设计有机长余辉发光材料的主流策略,该类材料主要集中在苯甲酸类、有机硼类化合物、氮杂芳环类化合物(咔唑、三苯胺、吩噻嗪等)几种结构的小分子上。
近年来,有机磷类化合物在电子传输材料及高效有机光电材料(特别是蓝光材料)方面取得了很好的成果。例如,许辉等设计了一系列含有三苯基氧膦的蓝光热激活延迟荧光化合物,有效地利用三线态激子实现高效发光,见文献:Gao F,Du R,Han C,Zhang J,WeiY,Lu G,Xu H.High-efficiency blue thermally activated delayed fluorescencefrom donor–acceptor–donor systems via the through-space conjugationeffect.Chem.Sci.,2019,10,5556-5567.;Li C,Duan C,Han C,Xu H.Secondary AcceptorOptimization for Full-Exciton Radiation:Toward Sky-Blue Thermally ActivatedDelayed Fluorescence Diodes with External Quantum Efficiency of≈30%.Adv.Mater.,2018,0(0):1804228.;Han C,Zhang Z,Ding D,Xu H.Dipole-DipoleInteraction Management for Efficient Blue Thermally Activated DelayedFluorescence Diodes.Chem,2018,4(9):2154-2167.。此类材料具有良好的稳定性、较高的荧光量子效率以及优良的电子传输性能,在OLEDs领域具有重要的应用价值。此外,含膦类有机发光材料在离子响应和氧气检测等领域也有广泛的应用。三苯基(氧)膦具有扭曲的结构,通过合理的分子设计,有目的地引入芳香基团,通过位阻效应稳定三线态激子,有望实现三苯基(氧)膦类化合物的长余辉发光,对有机长余辉材料种类的拓展和研究具有重要的意义。
发明内容
要解决的技术问题
为了避免现有技术的不足之处,本发明提出一种含三苯基(氧)膦的有机长余辉材料及制备方法和使用方法。
技术方案
一种含三苯基(氧)膦的有机长余辉材料,其特征在于:三苯基(氧)膦的2号位上接上芳香环或芳香杂环化合物R,结构通式为:
其中,R为芳香环或芳香杂环化合物。
所述R选自如下分子中的任意一种:
所述芳香环或芳香杂环化合物R结构中的R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14和R15相同或不同,各自独自地选自氢原子、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基中的任意一种。
一种所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将二苯基膦衍生物与含碘的芳香环或芳香杂环化合物以摩尔比1︰0.8~1︰3,在甲苯溶液中,以三乙胺为碱,在四三苯基膦钯【Pd(PPh3)4】催化下,加热回流进行偶联反应得到含三苯基(氧)膦的有机长余辉材料。
一种所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将将含溴或碘的三苯基膦衍生物与含硼酸或硼酸酯的芳香环或芳香杂环化合物以摩尔比1︰0.8~1︰3混合在四氢呋喃溶液中,以碳酸钾为碱,在二茂铁氯化钯【Pd(dppf)Cl2】催化下,加热回流通过Suzuki反应得到含三苯基(氧)膦的有机长余辉材料。
一种所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将2-二苯基膦苯甲醛及其衍生物与一端或两端含有亚磷酸酯的芳香环或芳香杂环化合物,在四氢呋喃溶液以摩尔比1︰0.8~1︰3混合,在叔丁醇钾作用下通过维悌希反应得到含三苯基(氧)膦的有机长余辉材料。
将所得的含三苯基(氧)膦的有机长余辉材料通过双氧水在四氢呋喃中氧化得到相应的氧膦类含三苯基(氧)膦的有机长余辉材料。
一种所述含三苯基(氧)膦的有机长余辉材料的使用方法,其特征在于:作为荧光探针用于生物成像。
一种所述含三苯基(氧)膦的有机长余辉材料的使用方法,其特征在于:作为长余辉材料用于防伪领域。
有益效果
本发明提出的一种含三苯基(氧)膦的有机长余辉材料及制备方法和使用方法,提供一种含三苯基(氧)膦的有机长余辉材料,提供多种合成方法,这些方法工艺简单,产率高,易于纯化,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。是结合时间分辨技术将所述有机长余辉材料应用于有机光电、生物成像和防伪等领域。
本发明所述含有三苯基(氧)膦的有机长余辉材料的分子结构TP(O)-R;其中,TP(O)为三苯基(氧)膦基团,R为芳香环或芳香杂环化合物,TP(O)和R基团通过临位相接,所合成的发光材料拥有螺旋形的分子构型,在大位阻构型和强分子内作用下有效地抑制非辐射跃迁,实现长余辉发光,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。此外,本发明结合时间分辨技术将所述有机长余辉材料应用于有机光电、生物成像和防伪等领域。
本发明的合成方法工艺简单,容易纯化,所合成的发光材料拥有螺旋形的分子构型,在大位阻构型和强分子内作用下有效地抑制非辐射跃迁,实现长余辉发光,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。此外,本发明结合时间分辨技术将所述有机长余辉材料应用于有机光电、生物成像和防伪等领域。
附图说明
图1是本发明实施例P1、P2的光致发光光谱:其中,黑色谱线是P1的稳态光谱曲线,灰色谱线是P2的稳态光谱曲线。
图2是本发明实施例P1和P2晶体的长余辉持续发光过程的发光照片
图3是本发明实施例P1的稳态光谱和延迟荧光光谱:其中,黑色谱线是P1的稳态光谱曲线,灰色谱线是P2的延迟光谱曲线。
图4是本发明实施例P2的稳态光谱和延迟荧光光谱:其中,黑色谱线是P2的稳态光谱曲线,深灰色谱线是P2的延迟较短时间的光谱曲线,浅灰色曲线是P2的延迟较长时间的光谱曲线。
具体实施方式
现结合实施例、附图对本发明作进一步描述:
实施例1:
(1)中间体【2-碘三苯胺】的合成
氮气氛围下,将二苯胺(2.00g,11.82mmol)加入250mL干燥三颈瓶中,再加入1,2-二碘苯(4.68g,14.18mmol),加入50mL甲苯溶解,加入邻菲罗啉(255.58mg,1.42mmol)、碘化亚铜(225.08mg,1.18mmol)和氢氧化钾(2.65g,47.27mmol),升温至110℃,搅拌反应16h。反应结束后,反应液经旋转蒸发去除甲苯,加入二氯甲烷50ml溶解,然后将反应液倒入分液漏斗,水洗2~3。将有机层用无水硫酸钠干燥,过滤,滤液在旋转蒸发仪中旋干,然后利用硅胶柱层析的方法进行提纯,淋洗液为体积比1:2的二氯甲烷和正己烷的混合溶液。得黄白色固体2.00g,产率45.6%。
(2)目标产物P1的合成
将2-碘三苯胺(1.00g,2.69mmol)溶于甲苯中,加入2mL三乙胺。加入二苯基膦(0.75g,4.04mmol)。升高温度至溶剂回流,加入四三苯基膦钯0.05g作为催化剂,搅拌回流36小时后将反应液冷却,抽滤,滤液用旋转蒸发仪蒸干。用硅胶柱层析的方法进行提纯,淋洗液为体积比1:1的二氯甲烷和正己烷的混合溶液。得纯产物0.73g,产率63.1%。
实施例2:
目标产物P2的合成
将实施例1(0.40g,0.93mmol)加入圆底烧瓶中,加入20ml四氢呋喃中溶解。加入6mL过氧化氢水溶液(30%),搅拌5小时后,在反应液中加入二氯甲烷、水各50ml后分液。将二氯甲烷层用旋转蒸发仪旋干,得白色粉末。将白色粉末用二氯甲烷/正己烷重结晶,得到白色固体0.35g,产率84.4%。
实施例3
(1)中间体2-溴三苯基膦的合成
参照实施例1中的步骤(2),利用邻溴碘苯代替2-碘三苯胺合成2-溴三苯基膦。(产率为59.2%)
(2)中间体2-溴三苯基氧膦的合成
参照实施例2中的步骤,利用2-溴三苯基膦代替2-二苯胺基三苯基膦合成2-溴三苯基氧膦。(产率为81.5%)
(3)目标产物2-(2-二苯氨基)苯基三苯基氧膦的合成
将2-硼酸酯基三苯胺(1.25g,3.36mmol)、2-溴三苯基氧膦(1.00g,2.80mmol)和氢氧化钠(0.34g,8.40mmol)加入250mL三口瓶中,加入适量乙二醇二甲醚,在氮气环境中加入一小勺四三苯基膦钯。升温至110℃,反应12h。之后将反应液冷却,加入二氯甲烷和水萃取,用二氯甲烷萃取3次,再用水洗3次。将有机层用无水硫酸钠干燥,在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯,淋洗液为体积比30:1的二氯甲烷和甲醇的混合溶液。得黄白色固体0.60g,产率41.1%。
综上所述,本发明所合成的发光材料拥有螺旋形的分子构型,在大位阻构型和强分子内作用下有效地抑制非辐射跃迁,实现长余辉发光,并可通过引入不同官能团进而调节终产物的发光波长、磷光寿命等性能。此外,本发明结合时间分辨技术将所述有机长余辉材料应用于有机光电、生物成像和防伪等领域。
Claims (9)
3.根据权利要求2所述含三苯基(氧)膦的有机长余辉材料,其特征在于:所述芳香环或芳香杂环化合物R结构中的R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14和R15相同或不同,各自独自地选自氢原子、烷基、卤素、烷氧基、硝基、氨基、醛基、氰基、苯基中的任意一种。
4.一种权利要求1~3任一项所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将二苯基膦衍生物与含碘的芳香环或芳香杂环化合物以摩尔比1︰0.8~1︰3,在甲苯溶液中,以三乙胺为碱,在四三苯基膦钯【Pd(PPh3)4】催化下,加热回流进行偶联反应得到含三苯基(氧)膦的有机长余辉材料。
5.一种权利要求1~3任一项所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将将含溴或碘的三苯基膦衍生物与含硼酸或硼酸酯的芳香环或芳香杂环化合物以摩尔比1︰0.8~1︰3混合在四氢呋喃溶液中,以碳酸钾为碱,在二茂铁氯化钯【Pd(dppf)Cl2】催化下,加热回流通过Suzuki反应得到含三苯基(氧)膦的有机长余辉材料。
6.一种权利要求1~3任一项所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将2-二苯基膦苯甲醛及其衍生物与一端或两端含有亚磷酸酯的芳香环或芳香杂环化合物,在四氢呋喃溶液以摩尔比1︰0.8~1︰3混合,在叔丁醇钾作用下通过维悌希反应得到含三苯基(氧)膦的有机长余辉材料。
7.根据权利要求4~6任一项所述含三苯基(氧)膦的有机长余辉材料的制备方法,其特征在于:将所得的含三苯基(氧)膦的有机长余辉材料通过双氧水在四氢呋喃中氧化得到相应的氧膦类含三苯基(氧)膦的有机长余辉材料。
8.一种权利要求1~3任一项所述含三苯基(氧)膦的有机长余辉材料的使用方法,其特征在于:作为荧光探针用于生物成像。
9.一种权利要求1~3任一项所述含三苯基(氧)膦的有机长余辉材料的使用方法,其特征在于:作为长余辉材料用于防伪领域。
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