CN113897193B - 一类基于二联芴类衍生物的蓝色发光材料 - Google Patents
一类基于二联芴类衍生物的蓝色发光材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 150000004826 dibenzofurans Chemical class 0.000 title claims abstract description 7
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 abstract description 10
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- 238000010129 solution processing Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 238000005859 coupling reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 27
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- -1 4-butoxy phenyl Chemical group 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 238000000103 photoluminescence spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- BOUVKHWPQNEXTO-UHFFFAOYSA-N 1-bromo-4-butoxybenzene Chemical compound CCCCOC1=CC=C(Br)C=C1 BOUVKHWPQNEXTO-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- OPCXXBLGKAKSOW-UHFFFAOYSA-N 2-bromo-9,9-bis(4-butoxyphenyl)fluorene Chemical compound BrC1=CC=2C(C3=CC=CC=C3C=2C=C1)(C1=CC=C(C=C1)OCCCC)C1=CC=C(C=C1)OCCCC OPCXXBLGKAKSOW-UHFFFAOYSA-N 0.000 description 2
- DJPKDXFWVXMORB-UHFFFAOYSA-N 2-bromo-9-(4-butoxyphenyl)fluoren-9-ol Chemical compound BrC1=CC=2C(C3=CC=CC=C3C=2C=C1)(O)C1=CC=C(C=C1)OCCCC DJPKDXFWVXMORB-UHFFFAOYSA-N 0.000 description 2
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QZUPHAGRBBOLTB-UHFFFAOYSA-N NSC 244302 Chemical compound C=1C=CC=CC=1P(C(C)(C)C)C1=CC=CC=C1 QZUPHAGRBBOLTB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 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 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QUBGBARTKXHDBT-UHFFFAOYSA-N 2-(9h-fluoren-2-yl)-9h-fluorene Chemical compound C1=C2CC3=CC=CC=C3C2=CC=C1C1=CC=C2C3=CC=CC=C3CC2=C1 QUBGBARTKXHDBT-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XNKVIGSNRYAOQZ-UHFFFAOYSA-N dibenzofluorene Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1CC1=CC=CC=C12 XNKVIGSNRYAOQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 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
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- C07F9/50—Organo-phosphines
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Abstract
本发明公开了一类基于二联芴类衍生物的蓝色发光材料,通过三(二亚苄基丙酮)二钯(0)催化的C‑H偶联反应将不同的吸电子基团引入二联芴的9号反应位点,得到一系列结构扭曲的蓝色发光材料;反应原料来源广,均为常见的有机小分子材料,合成成本低,便于产业化;所述发光材料的能隙较宽,发光波长稳定,热稳定性较好,荧光量子产率高,且在一般有机溶剂中都表现出较好的溶解性,适合通过溶液加工的方式制备相应的电致发光器件;该材料在固态薄膜状态下依然保持了优秀的蓝光发射,应用于有机电致发光器件则可以提高器件发光效率,保持蓝光发射,提高器件蓝光发射的色纯度和饱和度。
Description
技术领域
本发明涉及有机电致发光材料技术领域,具体涉及一类基于二联芴类衍生物的蓝色发光材料。
背景技术
从黑白屏到彩色屏,从曲面屏到折叠屏,个人通讯设备的快速发展以及近年来智能手机的更新换代让有机发光二极管(Organic Light Emission Diodes,OLEDs)技术从幕后走向了台前。随着各种智能电子设备的普及,OLED显示技术正在逐渐融入我们的日常生活。
对比其他主流显示技术,OLED显示屏因其自发光的特点导致其在器件响应、功耗和显示对比度等方面有着更为优异的表现。此外,在柔性显示和透明显示技术领域,OLED也展现出了更好的应用潜力。但是,目前的OLED显示技术仍有很大的进步空间,尤其是在大面积显示器件的制备中,其产品良品率和生产加工成本控制还有较长的一段路要走。
全彩显示依赖于屏幕中的红,绿,蓝三种颜色发光器件的表现。目前而言,红光和绿光器件在发光稳定性、发光效率以及器件寿命等方面已经可以达到人们的使用要求,唯有蓝光器件在平衡发光色纯度、发光效率和寿命等方面还有待进一步提高。
排除器件加工工艺和功能材料的影响,开发新的蓝光材料是提高器件发光能力最为有效和直接的办法。芴基团是一种宽带隙的平面分子,具有不错的热稳定性和较高的荧光量子产率,并且拥有多个可修饰化学反应位点,是一种用于研究高效蓝光材料的极为优异的基础单元。此外,相较于芴基聚合物由于聚合度的影响导致其实验可重复性低,芴基小分子的化学结构更为准确,而且小分子在物质成膜和溶解性方面优势较大,更有利于溶液加工的方式制备器件。
基于上述分析,我们设计了一类新的基于二联芴和不同吸电子基团的发光材料,该类材料具有良好的热稳定性和化学相容性,较高的发光量子效率以及优异的成膜能力,是一类高性能的有机蓝光小分子。
发明内容
OLED器件中,发光层材料作为器件的核心,其发光效率的高低直接决定了器件发光效率的上限。发光材料良好的载流子传输能力可以减少其它功能材料的使用,简化器件结构,更有利于器件的快速制备。此外,为降低器件的生产成本,提高器件良品率而选择的溶液加工方法对发光材料的溶解性也提出了一定的要求。为解决上述技术问题,本发明提供了一类基于二联芴类衍生物的蓝色发光材料,通过对分子的改性和结构调整可以增加材料的溶解性以及电荷传输能力,芴基团的高量子产率则使得其可作为发光材料,应用于可溶液加工的高效有机蓝光器件。
本发明公开一类基于二联芴类衍生物的蓝色发光材料,具有如通式I所示化学结构:
其中,L为C4-C8的烷氧基苯基,R为包括二苯基砜,三苯基氧膦,二苯甲酮在内的含氧原子且可起到桥联作用的吸电子基团。
进一步地,通式I的所示化合物取自下列中的任一种:
本发明的有益效果为:
两类基于二联芴基团的衍生物的表征分析结果显示,联芴结构的形成有助于增强分子的共轭结构,提高其热稳定性;
在芴的9号位碳原子上引入烷氧基链则可以增强分子的溶解性,实现溶液加工过程,降低OLED器件的制作成本;
此外,由于位阻效应,分子结构会产生一定的扭曲,降低了芴结构之间的相互作用,减少分子长波长的发射,保证了蓝光发射的稳定性;
联芴结构具有一定的给电子特性和空穴传输能力,其与吸电子基团的结合有助于改善其电子传输能力,使材料具备更好的载流子传输特性,从而减少器件中其他功能层的引入,简化器件结构。
附图说明
图1中,(a)是化合物DF、(DF)2SO2、(DF)2PO的DSC(a)测试曲线,(b)是化合物DF、(DF)2SO2、(DF)2PO的TGA(b);
图2为归一化的化合物(DF)2SO2(a)、(DF)2PO(b)和DF(c)在甲苯溶液(10-5M)中的紫外吸收-PL光谱(激发光330nm)、在2-甲基四氢呋喃溶液中的低温(77K)荧光和磷光光谱以及薄膜状态的PL光谱(激发光330nm);
图3为归一化三种化合物在六种不同极性溶剂(10-5M)中的UV-PL光谱(激发光330nm);
图4为化合物(DF)2SO2、(DF)2PO和DF在二氯甲烷溶液中的电化学氧化曲线;
图5为(DF)2SO2和(DF)2PO在有氧(无氧)状态下在甲苯溶液(10-5M)中的瞬态-延迟衰减曲线(激发光330nm)。
具体实施方式
以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。在不背离本发明实质的情况下,对本发明方法、步骤或条件所作的修改和替换,均属于本发明的范围。
实施例1:电子给体二联芴DF的合成路线如下
具体合成过程如下:
取两口烧瓶,加入对溴苯酚4.27g和无水碳酸钾6.63g,N,N-二甲基甲酰胺(DMF)33mL,溴代正丁烷3.3g,80℃反应10小时,得1-溴-4-丁氧基苯3.6g(产率66%)。
取两口烧瓶,将1-溴-4-丁氧基苯3.62g制备成格式试剂,加入2-溴芴酮3.1g,四氢呋喃60mL,65℃冷凝回流20小时,得2-溴-9-(4-丁氧基苯基)-9-芴醇4.4g(产率55%)。
取两口烧瓶,加入2-溴芴酮1.8g,苯酚6.6g,甲基磺酸10mL,50℃反应约20h,得白色粉末状产物1.87g。
取两口烧瓶,加入前一步所得白色粉末1.7g,无水碳酸钾0.62g,DMF 30mL,溴代正丁烷0.83g,65℃反应10小时,得2-溴-9,9-双(4-丁氧基苯基)-芴1.94g(产率70%)。
取两口烧瓶,加入2-溴-9,9-双(4-丁氧基苯基)-芴1g,联硼酸频那醇酯0.56g,乙酸钾0.2g,Pd(dppf)Cl2催化剂0.1g,1,4-二氧六环15mL,80℃冷凝回流约20小时,得2-(9,9-双(4-丁氧基苯基)-9H-芴-2-基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷0.4g(产率43%)。
取两口烧瓶,加入2-溴-9-(4-丁氧基苯基)-9-芴醇1.4g,2-(9,9-双(4-丁氧基苯基)-9H-芴-2-基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷1.8g,四-(三苯基膦)钯0.33g,2mol/L碳酸钾溶液11mL,甲苯30mL,90℃下冷凝回流20h,得9,9',9'-三(4-丁氧基苯基)-9,9'-H-[2,2'-二芴]-9-醇1.54g(产率70%)。
取两口烧瓶,加入9,9',9'-三(4-丁氧基苯基)-9,9'-H-[2,2'-二芴]-9-醇0.4g,二氯甲烷20mL,三乙基硅烷0.2mL,三氟化硼乙醚0.15mL,0℃反应2h,得电子给体二联芴DF0.3g(产率73%)。
1H NMR(400MHz,CDCl3,ppm)δ7.82(ddd,J=18.6,7.6,3.1Hz,4H),7.69–7.55(m,4H),7.46–7.35(m,4H),7.30(t,J=7.4Hz,2H),7.22(t,J=8.6Hz,4H),7.09(d,J=8.6Hz,2H),6.90–6.76(m,6H),5.09(s,1H),4.03–3.88(m,6H),1.78(tq,J=12.8,6.4Hz,6H),1.57–1.45(m,6H),1.01(dt,J=13.1,5.1Hz,9H)。13C NMR(101MHz,CDCl3,ppm)δ158.14,157.87,152.56,148.56,140.89,140.63,140.08,139.61,139.10,137.83,133.14,129.31,129.19,127.63,127.29,126.59,125.31,120.30,119.89,114.69,114.06,67.56,64.28,53.75,31.38,19.28,13.89。MALDI-TOF,m/z:理论值:775.04,实验值:774.592。
实施例2:化合物(DF)2SO2和(DF)2PO的合成路线如下
(DF)2SO2的制备:取反应试管,加入DF 1.5g(1.94mmol),4,4-二溴二苯砜0.2g,叔丁醇钾0.175g,叔丁基二苯基膦0.04g,三-(二亚苄基丙酮)二钯0.1g,甲苯4mL,110℃下反应30h,得产物(DF)2SO2 0.27g。
1H NMR(400MHz,CDCl3,ppm)δ7.77(dd,J=13.2,7.3Hz,12H),7.57(d,J=9.9Hz,4H),7.53–7.47(m,4H),7.38(q,J=8.0Hz,10H),7.34–7.28(m,4H),7.27(d,J=5.6Hz,1H),7.25–7.23(m,1H),7.18–7.13(m,8H),7.07(d,J=8.7Hz,4H),6.77(t,J=7.0Hz,12H),3.90(t,J=5.9Hz,12H),1.78–1.68(m,12H),1.50–1.42(m,12H),0.95(td,J=7.3,2.6Hz,18H)。13CNMR(101MHz,CDCl3,ppm)δ158.23,157.94,152.62,152.33,152.26,141.28,140.39,139.70,139.47,139.40,139.10,137.75,129.15,129.10,128.95,127.93,127.75,127.34,126.53,126.06,124.61,124.51,114.39,114.10,67.58,64.84,64.29,31.36,19.25,13.84。MALDI-TOF,m/z:理论值:1764.33,实验值:1764.259。
(DF)2PO的制备:取反应试管,加入DF 1.86g,双(4-溴苯基)(苯基)氧化膦0.44g,叔丁醇钾0.26g,叔丁基二苯基膦0.06g,三-(二亚苄基丙酮)二钯0.15g,甲苯溶液6mL,110℃下反应30h。得产物(DF)2PO 0.48g。
1H NMR(400MHz,CDCl3,ppm)δ7.79–7.71(m,8H),7.62(dd,J=11.5,7.7Hz,2H),7.57–7.45(m,13H),7.43–7.27(m,16H),7.24(d,J=1.5Hz,1H),7.13(dt,J=8.8,4.5Hz,9H),7.07(d,J=8.7Hz,4H),6.74(d,J=8.7Hz,12H),3.93–3.83(m,12H)。13C NMR(101MHz,CDCl3,ppm)δ158.14,157.95,152.60,152.25,151.46,151.10,150.66,141.13,140.63,139.72,139.54,139.34,139.24,137.84,136.76,132.37,132.17,132.07,130.95,129.17,128.88,128.49,128.33,128.21,127.82,127.73,127.37,126.99,126.62,126.20,126.09,124.66,114.13,67.58,64.95,64.30,31.38,30.62,19.28,13.87。MALDI-TOF,m/z:理论值:1824.35,实验值:1825.454。
结果表征:
本发明设计合成了一类具有高效蓝光发射的有机小分子材料,其基本构建骨架为烷氧基苯基修饰的二联芴类衍生物和两种具有桥联作用的吸电子基团。二联芴和两种终产物的分子结构通过质谱(MALDI-TOF)、核磁共振氢谱和碳谱进行表征确认。通过紫外-可见吸收光谱和光致发光光谱研究了化合物的光物理性质。通过差示扫描量热法和热重分析法研究了化合物的热稳定性,通过循环伏安法研究了化合物的电化学性质。
热稳定性能
通过差式扫描量热法(DSC)和热重分析法(TGA)测试了三种化合物的热稳定性,测试结果如图1所示:化合物DF、(DF)2SO2和(DF)2PO的玻璃化转变温度分别为75℃、66℃和73℃,质量损失为5%时的分析温度达到了383℃、429℃和375℃。三种化合物的玻璃化转变温度都在70℃左右,与DF相比,引入吸电子基团后的(DF)2SO2和(DF)2PO的分子链段柔性有所增强,所以它们的相转变温度也比DF要降低了一点。三种化合物在TGA测试中都展现出了比较高的热稳定性,这得益于二联芴部分较强的刚性共轭结构,并且吸电子基团的引入也并未对这样的刚性结构产生较大的影响。
光物理性能
为研究物质的发光特性,我们测试了DF、(DF)2SO2、(DF)2PO三种物质在甲苯溶液(10-5M)中的紫外吸收和发射光谱以及在薄膜和2-甲基四氢呋喃(77K)中的光致发光光谱。如图2所示,在甲苯溶液溶液中,三种化合物展现出了几乎一样的紫外吸收光谱,在330nm左右显示出最强吸收,这可归因于分子内部芴和苯环上较为活跃的π-π*跃迁。根据DF、(DF)2SO2、(DF)2PO吸收光谱中吸收峰起始位置计算出它们的能隙(Eg)分别为3.38eV、3.35eV和3.36eV。
化合物DF、(DF)2SO2、(DF)2PO在甲苯稀溶液中都展现出了较强的蓝光双峰发射,其发射峰波长依次为391/372nm,394/375nm、394/375nm,以短波长荧光发射峰计算出它们的S1能级为3.34eV、3.31eV和3.30eV。对比DF,引入吸电子基团形成的(DF)2SO2和(DF)2PO并没有表现出其他特别的发光现象,说明二苯砜和三苯基磷氧的引入对于DF的发光特性没有发生太大的影响。
测试了三种化合物的低温磷光光谱并根据磷光发射峰的短波方向起始位置计算出DF、(DF)2SO2、(DF)2PO的T1能级为2.68eV、2.35eV和2.34eV,可以看出吸电子基团的引入使得化合物的T1能级有了明显的降低。DF、(DF)2SO2、(DF)2PO三种分子在薄膜下都有单峰发射的倾向,其最高发射峰波长为407nm、410nm、402nm。与各物质本身在溶液状态下的发光情况相比,产生了约35nm的红移,这是由于固态分子聚集使得分子间相互作用增强所造成的的结果。但即便发生了红移,三种物质的发射依然属于蓝光发射区域,并且其发射光谱的半峰宽仅有40nm,表现出了较高的蓝光发射色纯度。
此外,测试了这三种分子在不同极性溶剂中的PL光谱,测试结果如图3所示。在所选的六种极性溶剂中,三种物质均表现出了比较不错的溶解性。随着溶剂极性由小变大,无论是紫外吸收光谱还是光致发光光谱,三种分子均未表现出较为明显和有规律的变化。所有的现象都说明DF、(DF)2SO2、(DF)2PO这三种材料不存在分子内电荷转移特性,而造成这一切的源头可能是这三种分子较为扭曲的分子空间结构。
电化学性质
为了分析三种化合物的能级结构,以二茂铁为内标物,六氟磷酸四丁铵为电解质通过循环伏安法测试了化合物(DF)2SO2、(DF)2PO和DF在二氯甲烷中的氧化曲线,结果如图4所示。在测试过程中三种化合物展现出了准可逆的氧化还原过程,表现出了不错的电化学稳定性。从图4中可以得知化合物(DF)2SO2、(DF)2PO和DF的初始氧化电位为0.92V、0.95V和0.79V,以此计算出三种化合物的HOMO能级为-5.75eV、-5.78eV和-5.62eV,联系前面计算出的三种化合物的能隙值就可以得出它们对应的LUMO能级为-2.40eV、-2.42eV和-2.24eV。对比化合物DF,吸电子基团的引入同时降低了分子的HOMO能级和LUMO能级,而LUMO能级的降低则使得材料中电子的注入与传输更加便利。
为探究合成的化合物的发光效率。通过稳态-瞬态荧光系统测试了化合物(DF)2SO2和(DF)2PO的瞬态-延迟衰减曲线。如图5所示,两种分子均属于荧光发射,其寿命在10ns左右。通过积分球计算出(DF)2SO2、(DF)2PO在甲苯溶液中的绝对发光量子产率为93.13%和91.59%(空气氛围)。结合材料在一般有机溶剂中的良好溶解性和稳定的蓝光发射,高发光效率的(DF)2SO2和(DF)2PO确实可以用来进行高效有机蓝光器件的制备。
以上显示和描述了本发明的基本原理、主要特征及优点。但是以上所述仅为本发明的具体实施例,本发明的技术特征并不局限于此,任何本领域的技术人员在不脱离本发明的技术方案下得出的其他实施方式均应涵盖在本发明的专利范围之中。
Claims (1)
1.一类基于二联芴类衍生物的蓝色发光材料,其特征在于,其结构为下述中的任意一种:
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