CN110790629A - 一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用 - Google Patents
一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用 Download PDFInfo
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- CN110790629A CN110790629A CN201911105496.8A CN201911105496A CN110790629A CN 110790629 A CN110790629 A CN 110790629A CN 201911105496 A CN201911105496 A CN 201911105496A CN 110790629 A CN110790629 A CN 110790629A
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- chiral
- substituted
- unsubstituted
- isomer
- spirofluorene
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Abstract
本发明涉及一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用,所述手性螺芴异构体包括式I中所示的R型异构体和S型异构体,本发明首次发现了式I所示的手性螺芴化合物异构体能够应用于具备手性关联功能的电子元器件中,这是由于R/S手性螺芴结构对映体具有±90℃的偏转面,可以更好的诱导固体薄膜中二级、三级结构的手性,从而得到可以产生圆偏振光的功能薄膜,并制备圆偏振光器件。
Description
技术领域
本发明涉及圆偏振发光技术领域,尤其涉及一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用,特别涉及一种手性螺芴异构体在圆偏振光器件中的应用。
背景技术
光是一种电磁波,属于横波的一种,光波振动方向与其传播方向垂直,这种在方向上的不对称被称为偏振,偏振光就是具有偏振性质的光。偏振光按照光波电矢量的振动方向轨迹的差别主要分为线偏振光、椭圆偏振光和圆偏振光。光波电矢量的振动方向形成的轨迹是一个圆,我们就把它称为圆偏振光,光波电矢量前进过程中方向随时间有规律的变化,同时其振幅大小保持不变。按照光矢量随着前进方向的旋转方向不同,我们又可以把圆偏振光分为左旋圆偏振光和右旋圆偏振光。圆偏振光可以用来表征手性物质的某些特征手性结构,如圆二色光谱(CD),它利用手性物质对左旋和右旋圆偏振光的吸收不同来表征化合物的手性结构和基态的电子手性特征。圆偏振发光就是一个手性发光体系可以发出不同的强度左旋和右旋圆偏振光的现象,它可以用来研究手性物质的激发态的手性特性,圆偏振发光的不对称程度由不对称因子glum来衡量,glum值可由glum=2(IL-IR)/(IL+IR),此计算得到,其中IL和IR分别代表左旋和右旋圆偏振光的强度,glum最大可达到2,其大小范围在[-2,2]。
圆偏振光可以通过有有机分子体系发光,或者在手性功能分子掺杂的发光器件得到。(综述文献:李猛、林伟彬、房蕾、陈传峰,手性有机小分子圆偏振发光的研究进展,化学学报Acta Chim.Sinica2017,75,1150-1163)。
更具体地,106831449B公开了一种具有上转换圆偏振发光的三重态受体材料及其制备方法和应用,该材料由于具有手性结构,并且在结构中含有并苯结构,使得该材料能够用作三重态湮灭上转换体系的能量受体,可与能量给体配合实现光子上转换并发射圆偏振光的目的,该三重态受体材料在手性光催化、生物显像、光信息的处理、显示和存储等方面具有较大的应用价值。
但是能够用于原偏振发光的手性有机小分子化合物的种类较少,随着圆偏振器件的迅速发展,这些手性有机小分子化合物难以满足现有的需求。
因此,本领域亟待开发更多种类的手性有机小分子在圆偏振器件中的应用。
发明内容
针对现有技术的不足,本发明的目的在于提供一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用,特别在于提供一种手性螺芴异构体在圆偏振光器件中的应用。
为达此目的,本发明采用如下技术方案:
本发明提供一种手性螺芴异构体在圆偏振光器件中的应用,所述手性螺芴异构体包括式I中所示的异构体R和异构体S;
式I中,所述m和n各自独立地为0~4的整数,例如1、2或3等,且m和n不同时为0;
式I中,所述A和B各自独立地选自氢、氘、氚、氟、18F同位素、氯、溴、碘、氰基、取代或未取代的C1~C12烷基、取代或未取代的C1~C12烯基、取代或未取代的C1~C12炔基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基、取代或未取代的羟基、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基、氨基胺基、C1~C12烷基取代的氨基、取代或未取代的C12~C30芳胺基、取代或未取代的巯基、取代或未取代的硅基、磷酸酯基、磺酰基中的任意一种,且A和B为不同的基团;
当上述基团存在取代基时,所述取代基选自氘、氚、氟、氯、溴、碘、氰基、羟基、氨基、C1~C12烷基、C1~C12烷氧基、C6~C30芳基、C3~C30杂芳基、C6~C30芳氧基、C12~C30芳胺基中的任意一种或至少两种组合;本发明涉及到“取代或未取代”的表述方法时,取代时取代基的选择均为上述基团,下文不一一赘述。
其中,虚线代表镜面。
本发明中,R/S分别代表以IUPAC化学结构命名法中单一对映体构型的顺时针方向旋转(R)和逆时针方向旋转(S)的两种构型。
本发明首次发现了式I所示的手性螺芴化合物的异构体(R或S)能够应用于圆偏振器件中,这是由于R/S手性螺芴结构对映体具有±90°的偏转面,可以更好的诱导固体薄膜中二级、三级结构的手性,从而得到可以产生圆偏振光的功能薄膜,并制备圆偏振光器件。
优选地,式I所示的手性螺芴的代表合成方法如下:
(1)
以2-氨联苯作原料,通过Sandmeyer反应得到2-碘联苯。再用2-碘联苯的Grignard试剂与9-芴酮合成制备9-(2-联苯基)-9-芴醇。然后生成的叔醇以醋酸为溶剂,以浓盐酸为催化剂并回流的反应条件下,进行关环反应得到目标产物9,9-螺二芴。HAc代表醋酸,acid代表酸试剂,Et2O代表乙醚。
(2)硫酸作催化剂合成卤化物:在室温下按照1:8:6:6的比例分别加入螺二芴、NaX、H2O2、浓度为10%的稀硫酸,反应48小时可得到目标产物。
(3)将上述产物通过Williamson合成、Schiemann反应、氘代等方法制备成目标消旋化合物。
(4)采用高效液相色谱(HPLC)法,使用液质联用分析设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物R和S。
上述方法中选择了一种未取代有A和B基团的化合物进行举例说明,本领域技术人员可以在上述方法的基础上,通过对原料的选择来制备得到含有A和/或B取代的化合物,或者通过现有技术的方法在中间产物中引入A和/或B基团。
优选地,所述m和n各自独立地为0或1,且m和n不同时为0。
优选地,所述手性螺芴异构体包括式II至式IX中所示的异构体R和异构体S;
其中,虚线代表镜面。
本发明优选上述几种特定取代基个数和位置的化合物,这些化合物应用于圆偏振光器件时,能够进一步提升器件的性能。
优选地,所述A和B各自独立地选自C1~C12氘代烷基、C6~C30氘代芳基、C1~C12氘代烷氧基、C6~C30氘代芳氧基、C6~C30氘代芳胺基、C1~C12烷氘代烷基取代的氨基、C1~C12烷氘代烷基取代的巯基、C6~C30氘代芳基取代的巯基、C1~C12氘代烷基取代的硅基、C1~C12氘代烷氧基取代的硅基、C6~C30氘代芳基取代的硅基、氘代有机金属取代基、氘代膦基、氘代磷酸酯基、氘代磺酰基中的任意一种。
优选地,所述A取代在2位。
优选地,所述A选自氢原子、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基和取代或未取代的C12~C30芳胺基中的任意一种。
优选地,所述A取代在2位,且所述A选自氢原子、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基和取代或未取代的C12~C30芳胺基中的任意一种。
优选地,所述B取代在2'位。
优选地,所述B选自氢原子、氰基和氰基取代的C6~C30芳基中的任意一种。
优选地,所述B取代在2’位,且B选自氢原子、氰基和氰基取代的C6~C30芳基中的任意一种。
优选地,所述手性螺芴异构体包括式Ⅲa至式Ⅲd中所示的异构体R和异构体S;
所述FG选自取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳基中的任意一种;
所述WFG选自氟、氰基,取代或未取代的吡啶基、取代或未取代的二嗪基、取代或未取代的三嗪基、取代或未取代的咪唑基、取代或未取代的吡唑基、取代或未取代的三氮唑基、取代或未取代的砜基中任意一种;
所述Ar1和Ar2各自独立地选自取代或未取代的C6~C30芳基;
所述π选自取代或未取代的亚乙烯基、取代或未取代的亚乙炔基、取代或未取代的苯基、取代或未取代的C3~C30氮杂芳基、取代或未取代的C10~C30稠环芳基中的任意一种;
其中,虚线代表镜面。
进一步的,本发明优选上述特定取代基取代的螺芴化合物异构体,应用圆偏振器件中,能够更进一步的提升器件发光的圆偏振特性。
优选地,所述手性螺芴异构体包括M1-M40中所示的异构体R和异构体S:
优选地,所述具备手性关联功能的电子元器件包括圆偏振光器件。
优选地,所述具备手性关联功能的电子元器件包括圆偏振光电致发光器件、手性分子开关器、手性场效应晶体管器件和手性分子探针器件中的任意一种。
优选地,所述圆偏振光器件中含有手性光学膜,所述手性光学膜中含有所述手性螺芴异构体。
优选地,所述圆偏振光器件中含有有机功能层,所述有机功能层中含有所述手性螺芴异构体。
优选地,所述有机功能层包括发光层、电荷传输层、电荷注入层和光改性层中的任意一种或至少两种组合。
优选地,所述发光层中含有所述手性螺芴异构体。
优选地,所述手性螺芴异构体作为发光层的发光材料、主体材料或客体材料。
在本发明的一个具体实施方式中,提供了一种有机电致发光器件,其结构如图13所示,图13显示了有机光电装置发光器件的断面图,该器件包含本发明所述的手性螺芴异构体。器件包括玻璃基底、氧化铟锡阳极层、空穴传输层、发光层、电子传输层和铝/氟化锂阴极层。发光层可以是包括一发射体和一主体的发光材料。
相较于现有技术,本发明采用如下技术效果:
本发明首次发现了式I所示的手性螺芴化合物的异构体(R或S)能够应用于圆偏振器件中,这是由于R/S手性螺芴结构对映体具有±90°的偏转面,可以更好的诱导固体薄膜中二级、三级结构的手性,从而得到可以产生圆偏振光的功能薄膜,并制备圆偏振光器件。
附图说明
图1是本发明具体实施方式中M2R和M2S的HPLC分析图。
图2a是本发明具体实施方式中M4R和M4S的HPLC分析图。
图2b是本发明具体实施方式中M4R的手性拆分图。
图2c是本发明具体实施方式中M4S的手性拆分图。
图3a是本发明具体实施方式中M6R和M6S的HPLC分析图。
图3b是本发明具体实施方式中M6R的手性拆分图。
图3c是本发明具体实施方式中M6S的手性拆分图。
图4a是本发明具体实施方式中M16R和M16S的HPLC分析图。
图4b是本发明具体实施方式中M16R的手性拆分图。
图4c是本发明具体实施方式中M16S的手性拆分图。
图5a是本发明具体实施方式中M31R和M31S的HPLC分析图。
图5b是本发明具体实施方式中M31R的手性拆分图。
图5c是本发明具体实施方式中M31S的手性拆分图。
图6a是本发明具体实施方式中M32R和M32S的HPLC分析图。
图6b是本发明具体实施方式中M32R的手性拆分图。
图6c是本发明具体实施方式中M32S的手性拆分图。
图7a是本发明具体实施方式中M33R和M33S的HPLC分析图。
图7b是本发明具体实施方式中33R的手性拆分图。
图7c是本发明具体实施方式中33S的手性拆分图。
图8是本发明具体实施方式中M16R在薄膜中的紫外可见吸收光谱图和发光光谱图。
图9是本发明具体实施方式中M16S在薄膜中的紫外可见吸收光谱图和发光光谱图。
图10a是本发明具体实施方式中M16R薄膜的形貌图。
图10b是本发明具体实施方式中M16R薄膜的形貌图的局部放大图。
图11a是本发明具体实施方式中M16R和M16S在薄膜中的圆偏振发光光谱图。
图11b是本发明具体实施方式中M31R和M31S在薄膜中的圆偏振发光光谱图。
图11c是本发明具体实施方式中M40R和M40S在薄膜中的圆偏振发光光谱图。
图11d是本发明具体实施方式中M16R薄膜在左偏振光和右偏振光下的荧光强度差异图。
图12a是本发明具体实施方式中M16R和M16S在薄膜中的不对称因子值变化图。
图12b是本发明具体实施方式中M31R和M31S在薄膜中的不对称因子值变化图。
图12c是本发明具体实施方式中M40R和M40S在薄膜中的不对称因子值变化图。
图13是本发明一个具体实施方式中的有机电致发光器件的断面图。
图14是钙钛矿底发光器件结构图。
图15a是实施例20中钙钛矿发光器件的外量子效率图。
图15b是实施例20中钙钛矿发光器件的电致发光光谱图。
图16a是实施例21中OLED发光器件光致发光光谱图。
图16b是实施例21中OLED发光器件发光亮度-电压图。
图17a是实施例22中OLED发光器件光致发光光谱图。
图17b是实施例22中OLED发光器件外量子效率与电流强度图。
图17c是实施例22中OLED发光器件发光亮度-电压图。
图17d是实施例22中OLED发光器件的圆偏振光光谱图。
图17e是实施例22中OLED发光器件的不对称因子值变化图。
具体实施方式
为便于理解本发明,本发明列举实施例如下。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
合成例1手性螺芴异构体M1R&M1S的制备
步骤一:2,2'-二羟基-9,9-螺二芴(400mg,1.14mmol)溶于无水二氯甲烷(75mL)与三乙胺(0.8mL,5.7mmol)充分混合,将混合物冷却至-10℃。三氟甲磺酸酐(0.5mL,2.9mmol)溶解于无水二氯甲烷(25mL)中,然后在1-2小时内滴完。加完后,将反应混合物在-10℃下搅拌1小时。将混合物温度回复至室温并在该温度下搅拌15小时,然后通过倒入冰冷的盐酸(5%)来淬灭反应。分离各层,水相用二氯甲烷萃取三次。将合并的有机层用饱和碳酸氢钠洗涤。有机相用无水硫酸钠干燥,减压蒸发溶剂至干。所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(5:1,v/v)作为洗脱剂。得到纯产物,为无定形白色树脂状固体(2,2'-双(三氟甲基亚磺酰氧基)-9,9'-螺二芴690mg,98%)。
步骤二:将2,2'-双(三氟甲基亚磺酰氧基)-9,9'-螺二芴(153mg,0.25mmol)和1,3-双(二苯基膦丙烷)二氯化镍(14mg,10mol%)在无水情况下反复抽空并用氩气填充。用注射器加入无水乙醚(25mL)。将体系冷却至0℃后,在约15分钟内滴加甲基溴化镁的乙醚溶液(3M,1mL,3mmol)。加完后,将反应混合物加热回流24小时。小心地将混合物在0℃下用水淬灭,然后用盐酸水稀释(5%)。将水层用乙醚萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(5:1,v/v)作为洗脱剂。得到纯产物,为白色固体(2,2'-二甲基-9,9'-螺二芴84mg,98%)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M1R和M1S。
核磁1HNMR(CDCl3,500.1MHz)δ=2.20(s,6H),6.54(s,2H),6.70(d,J=7.7Hz,2H),7.07(ddd,J=7.7,7.7,1.1Hz,2H),7.17(m,2H),7.34(ddd,J=7.7,7.7,1.1Hz,2H),7.72(d,J=7.7Hz,2H),7.79(d,J=7.7Hz,2H)ppm。
13CNMR(125.8MHz,CDCl3)δ=21.5,65.7,119.6,119.6,124.0,124.6,127.3,127.5,128.5,137.8,139.1,141.8,148.9,149.2ppm。
质谱HR-MS(Maldi)计算值C27H21[M+]:345.1643,测试值:345.1622。
其中,M1R和M1S分别代表化合物M1的异构体R和异构体S。
合成例2手性螺芴异构体M2R&M2S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),二苯胺(0.76g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(toluene,10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用硫酸镁干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:82.9%(0.8g)。
采用高效液相色谱(HPLC)法,使用的手性制备色谱柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物2R和2S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/EtOH=50/50(V/V)为流动相,UV254nm检测,结果如图1所示,化合物M2R和化合物M2S的出峰时间分别为6.904min和7.662min。
核磁1H NMR(300MHz,DMSO)δ7.81(d,J=8.0Hz,2H),7.33(t,J=7.4Hz,1H),7.22(t,J=7.6Hz,5H),7.08(d,J=6.5Hz,1H),7.01(d,J=7.4Hz,2H),6.88(d,J=7.8Hz,4H),6.63(d,J=7.5Hz,1H),6.28(s,1H).
质谱HR-MS(Maldi)计算值C49H34N2[M+]:650.27,测试值:650.27。
合成例3手性螺芴异构体M3R&M3S的制备
将2,2'-双(三氟甲基亚磺酰氧基)-9,9'-螺二芴(153mg,0.25mmol)和1,3-双(二苯基膦丙烷)二氯化镍(14mg,10mol%)在无水情况下反复抽空并用氩气填充。用注射器加入无水乙醚(25mL)。将体系冷却至0℃后,在约15分钟内滴加异丙基基溴化镁的乙醚溶液(3M,1mL,3mmol)。加完后,将反应混合物加热回流24小时。小心地将混合物在0℃下用水淬灭,然后用盐酸水稀释(5%)。将水层用乙醚萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(5:1,v/v)作为洗脱剂。得到纯产物,为白色固体(2,2'-二甲基-9,9'-螺二芴84mg,98%)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M3R和M3S。
质谱HR-MS(Maldi)计算值C32H19[M+]:413.23,测试值:413.23。
合成例4手性螺芴异构体M4R&M4S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),3-甲基二苯胺(0.82g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:82.9%(0.8g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M4R和M4S。
分析采用0.46cm I.D.×15cm L手性柱,MeOH/DCM=80/20(V/V)为流动相,UV254nm检测,测试结果如图2a-2c所示,图2a显示化合物M4R和化合物M4S的出峰时间分别为2.601min和3.267min,其中,特征峰面积分布数据如下表所示:
特征峰 | 保留时间(min) | 峰面积 | 峰面积占比(%) |
1 | 2.601 | 2685060 | 48.797 |
2 | 3.000 | 29816 | 0.542 |
3 | 3.267 | 2787646 | 50.661 |
图2b和2c显示制备化合物M4R和化合物M4S时的出峰时间分别为2.606min和3.270min及纯度分别为99.579%和96.952%,即得到光学异构体的纯品化合物M4R和M4S。
核磁1H NMR(500MHz,DMSO)δ7.84–7.75(m,4H),7.33(t,J=7.5Hz,2H),7.21(t,J=7.7Hz,4H),7.09(dt,J=11.3,5.5Hz,4H),6.99(t,J=7.1Hz,2H),6.89(t,J=8.3Hz,6H),6.80(d,J=7.4Hz,2H),6.71(s,2H),6.64(t,J=7.2Hz,4H),6.29(s,2H),2.12(s,6H)。
质谱HR-MS(Maldi)计算值C51H38N2[M+]:678.30,测试值:678.32。
合成例5手性螺芴异构体M5R&M5S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),氰化亚铜(0.53g,5.92mmol),在N,N-二甲基甲酰胺(15mL)溶液中充分混合,在130℃加热并搅拌20小时。冷却至室温后,用水淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(5:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:95%(0.5g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M5R和M5S。
1HNMR(CDCl3,500.1MHz)δ=6.74(dd,J=7.7,1.1Hz,2H),6.95(d,J=1.5Hz,2H),7.24(ddd,J=7.7,7.7,1.1Hz,2H),7.46(ddd,J=7.7,7.7,1.1Hz,2H),7.70(dd,J=7.7,1.5Hz,2H),7.91(d,J=7.7Hz,2H),7.96(d,J=7.7Hz,2H)ppm。
13CNMR(125.8MHz,CDCl3)δ=65.5,111.2,118.7,120.9,121.4,124.2,127.6,128.8,130.0,132.6,139.8,146.2,147.8,148.1ppm。
质谱HR-MS(Maldi)计算值C27H14N2[M+]:366.12,测试值:366.12。
合成例6手性螺芴异构体M6R&M6S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),N-苯基-1-萘胺(0.97g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:96%(1.0g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M6R和M6S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/EtOH=50/50(V/V)为流动相,UV254nm检测,测试结果如图3a-3c所示,图3a显示化合物M6R和化合物M6S出峰时间分别为3.624min和4.331min,其中,特征峰面积分布数据如下表所示:
图3b和3c显示制备化合物M6R和化合物M6S时的出峰时间分别为3.648min和4.390min及纯度分别为99.647%和99.699%,即得到光学异构体的纯品化合物M6R和M6S。
核磁1H NMR(300MHz,CDCl3)δ7.75–7.68(m,1H),7.67–7.55(m,3H),7.53–7.46(m,1H),7.39–7.31(m,3H),7.26(s,2H),7.18(dt,J=8.4,5.2Hz,3H),7.12–6.93(m,5H),6.77(d,J=7.5Hz,1H),6.71(d,J=1.9Hz,1H).
质谱HR-MS(Maldi)计算值C57H38N2[M+]:750.30,测试值:750.32。
合成例7手性螺芴异构体M8R&M8S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),N-苯基-2-萘胺(0.97g,4.4mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:96%(1.0g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M8R和M8S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/EtOH=50/50(V/V)为流动相,UV254nm检测,化合物M8R和化合物M8S出峰时间分别为6.904min和7.662min。
核磁1H NMR(300MHz,CDCl3)δ7.75–7.68(m,1H),7.67–7.55(m,3H),7.53–7.46(m,1H),7.39–7.31(m,3H),7.26(s,2H),7.18(dt,J=8.4,5.2Hz,3H),7.12–6.93(m,5H),6.77(d,J=7.5Hz,1H),6.71(d,J=1.9Hz,1H).
质谱HR-MS(Maldi)计算值C57H38N2[M+]:750.30,测试值:750.32。
合成例8手性螺芴异构体M10R&M10S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),N-(3-甲基苯基)萘-2-胺(1.03g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:96%(1.0g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M10R和M10S。
质谱HR-MS(Maldi)计算值C59H42N2[M+]:778.33,测试值:778.32。
合成例9手性螺芴异构体M16R&M16S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),双(3-甲氧基苯基)胺(1.01g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:95%(1.08g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M16R和M16S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/DCM=70/30(V/V)为流动相,UV254nm检测,结果如图4a-4c所示,图4a中显示化合物M16R和化合物M16S的出峰时间分别为4.036min和4.407min,其中,特征峰面积分布数据如下表所示:
特征峰 | 保留时间(min) | 峰面积 | 峰面积占比(%) |
1 | 4.036 | 2332331 | 50.0098 |
2 | 4.407 | 2331421 | 49.9902 |
图4b和4c显示制备化合物M16R和化合物M16S时的出峰时间分别为4.022min和4.084min及纯度分别为99.0692%和99.0459%,即得到光学异构体的纯品化合物M16R和M16S。
核磁1H NMR(300MHz,CDCl3)δ7.83(d,J=8.1Hz,4H),7.35(t,J=7.5Hz,2H),7.11(dd,J=16.8,8.6Hz,6H),6.94(dd,J=8.3,2.0Hz,2H),6.68–6.54(m,6H),6.50–6.30(m,10H),3.56(s,12H).
质谱HR-MS(Maldi)计算值C53H42N2O4[M+]:770.31,测试值:770.32。
合成例10手性螺芴异构体M17R&17S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL二甲基亚砜的反应管中,加入490mg碳酸钾,16mg四叔丁基溴化铵以及820mg 1-(2-溴乙氧基)芘,氮气保护下,加热回流,反应20小时后,通过TCL检测原料消失,即反应结束。温度降至室温,产物直接析出,用乙酸乙酯清洗得到白色固体产物,产率95%(0.79g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M17R和M17S。
核磁1HNMR(400MHz,)δ8.34(d,J=9.2Hz),8.04(dd,J=10.2,8.1Hz),7.97–7.93(m),7.93–7.92(m),7.91(s),7.85(d,J=9.0Hz),7.75–7.71(m),7.44(d,J=8.4Hz),7.34–7.30(m),7.02(td,J=7.5,1.0Hz),6.93(dd,J=8.4,2.4Hz),6.72–6.68(m),6.33(d,J=2.3Hz),4.25(t,J=6.0Hz),3.88(t,J=6.0Hz),2.02(dd,J=12.6,6.8Hz),1.95(dd,J=13.8,5.9Hz).
质谱HR-MS(Maldi)计算值C61H40O4[M+]:836.29,测试值:836.28。
合成例11手性螺芴异构体M18R&M18S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL 5%氢氧化钠水溶液的反应管中,16mg四叔丁基溴化铵以及812mg 1-(4-溴丁氧基)芘,氮气保护下,加热回流,反应20小时后,通过TCL检测原料消失,即反应结束。温度降至室温,产物直接析出,用二甲基亚砜在80摄氏度下清洗得到产物,产率95%(0.85g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M18R和M18S。
核磁1HNMR(400MHz,)δ8.34(d,J=9.2Hz),8.04(dd,J=10.2,8.1Hz),7.97–7.93(m),7.93–7.92(m),7.91(s),7.85(d,J=9.0Hz),7.75–7.71(m),7.44(d,J=8.4Hz),7.34–7.30(m),7.02(td,J=7.5,1.0Hz),6.93(dd,J=8.4,2.4Hz),6.72–6.68(m),6.33(d,J=2.3Hz),4.25(t,J=6.0Hz),3.88(t,J=6.0Hz),2.02(dd,J=12.6,6.8Hz),1.95(dd,J=13.8,5.9Hz).
质谱HR-MS(Maldi)计算值C65H48O4[M+]:892.36,测试值:892.37。
合成例12手性螺芴异构体M19R&M19S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL 5%氢氧化钠水溶液的反应管中,16mg四叔丁基溴化铵以及955mg 1-((6-溴己基)氧基)芘,氮气保护下,加热回流,反应20小时后,通过TCL检测原料消失,即反应结束。温度降至室温,产物直接析出,用二甲基亚砜在80摄氏度下清洗得到产物,产率90%(0.85g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M19R和M19S。
核磁1HNMR(400MHz,)δ8.40(d,J=9.2Hz),8.06(dd,J=8.3,3.2Hz),7.98(s),7.96–7.90(m),7.86(d,J=9.0Hz),7.72(d,J=8.7Hz),7.69(s),7.50–7.45(m),7.34–7.29(m),7.04–6.99(m),6.89(dd,J=8.4,2.4Hz),6.69(d,J=7.5Hz),6.29(d,J=2.3Hz),4.25(t,J=6.3Hz),3.77(t,J=6.3Hz),1.53–1.42(m),0.88–0.80(m).
质谱HR-MS(Maldi)计算值C61H40O4[M+]:836.29,测试值:836.28。
合成例13手性螺芴异构体M21R&M21S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL甲苯的反应管中,加入9mg醋酸钯,425mg磷酸钾,25mg三叔丁基膦以700mg 1-溴芘,氮气保护下,加热回流,反应36小时后,通过TCL检测原料消失,即反应结束。温度降至室温,将反应液倒入乙酸乙酯中萃取,有机相使用无水碳酸钠干燥,旋干溶剂,通过柱色谱分离得到产物,产率60%(0.45g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M21R和M21S。
核磁1HNMR(400MHz,)δ8.33(d,J=9.2Hz),8.18–8.13(m),8.06–7.98(m),7.76–7.70(m),7.52–7.46(m),7.38–7.33(m),7.14(td,J=7.5,1.1Hz),6.98–6.95(m),6.85–6.81(m),6.75(d,J=2.2Hz).
质谱HR-MS(Maldi)计算值C57H32O2[M+]:748.24,测试值:748.24。
合成例14手性螺芴异构体M22R&M22S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL甲苯的反应管中,加入9mg醋酸钯,425mg磷酸钾,25mg三叔丁基膦以700mg 2-溴芘,氮气保护下,加热回流,反应36小时后,通过TCL检测原料消失,即反应结束。温度降至室温,将反应液倒入乙酸乙酯中萃取,有机相使用无水碳酸钠干燥,旋干溶剂,通过柱色谱分离得到产物,产率60%(0.45g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M22R和M22S。
质谱HR-MS(Maldi)计算值C57H32O2[M+]:748.24,测试值:748.24。
合成例15手性螺芴异构体M25R&M25S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL甲苯的反应管中,加入9mg醋酸钯,425mg磷酸钾,25mg三叔丁基膦以707mg 2-溴-7-叔丁基芘,氮气保护下,加热回流,反应36小时后,通过TCL检测原料消失,即反应结束。温度降至室温,将反应液倒入乙酸乙酯中萃取,有机相使用无水碳酸钠干燥,旋干溶剂,通过柱色谱分离得到产物,产率60%(0.50g)。采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M25R和M25S。
质谱HR-MS(Maldi)计算值C65H48O2[M+]:860.37,测试值:860.37。
合成例16手性螺芴异构体M26R&26S的制备
称取346mg(R)-2,2’-二羟基-9,9’-螺二芴,加入盛有10mL甲苯的反应管中,加入9mg醋酸钯,425mg磷酸钾,25mg三叔丁基膦以707mg 1-溴-7-叔丁基芘,氮气保护下,加热回流,反应36小时后,通过TCL检测原料消失,即反应结束。温度降至室温,将反应液倒入乙酸乙酯中萃取,有机相使用无水碳酸钠干燥,旋干溶剂,通过柱色谱分离得到产物,产率60%(0.50g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M26R和M26S。
质谱HR-MS(Maldi)计算值C65H48O2[M+]:860.37,测试值:860.25。
合成例17手性螺芴异构体M31R&M31S的制备
称取642mg 2,2-二溴-9,9-螺二芴,加入盛有10mL乙二醇二甲醚(DME)和10mL水的反应管中,加入162mg四三苯基膦钯,279mg碳酸钾以及2.5g原料,氮气保护下,加热回流,反应12小时后,通过TCL检测原料消失,即反应结束。温度降至室温,将反应液倒入乙酸乙酯中萃取,有机相使用无水碳酸钠干燥,旋干溶剂,通过柱色谱分离得到产物,产率90%。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M31R和M31S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/DCM=90/10(V/V)为流动相,UV254nm检测,结果如图5a-5c所示,图5a显示化合物M31R和化合物M31S的出峰时间分别为3.674min和3.4618min,其中,特征峰面积分布数据如下表所示:
特征峰 | 保留时间(min) | 峰面积 | 峰面积占比(%) |
1 | 3.674 | 2734982 | 49.688 |
2 | 4.618 | 2769312 | 50.312 |
图5b和5c显示制备化合物M31R和化合物M31S时的出峰时间分别为3.684min和4.689min及纯度分别为99.134%和99.142%,即得到光学异构体的纯品化合物M31R和M31S。。
核磁1H NMR(300MHz,DMSO)δ7.95(dd,J=7.7,3.8Hz,4H),7.42–7.31(m,4H),7.15(t,J=7.8Hz,8H),7.04(dd,J=14.5,7.0Hz,6H),6.95–6.89(m,12H),6.72(dd,J=13.2,8.2Hz,12H),6.57(d,J=7.7Hz,2H),6.45(s,2H),6.32(d,J=1.8Hz,4H),6.26(s,2H),2.10(s,12H).
质谱HR-MS(Maldi)计算值C89H68N4[M+]:1192.54,测试值:1192.55。
合成例18手性螺芴异构体M32R&M32S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),双(4-甲氧基苯基)胺(1.01g,4.44mmol),醋酸钯(18mg,0.082mmol),碳酸铯(1.74g,5.33mmol)和三叔丁基膦(0.038mL,0.15mmol)在甲苯(10mL)溶液中充分混合,在110℃加热并搅拌20小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:95%(1.08g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M32R和M32S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/THF=70/30(V/V)为流动相,UV254nm检测,测试结果如图6a-6c所示,图6a显示化合物M32R和化合物M32S的出峰时间分别为4.801min和6.268min,其中,特征峰面积分布数据如下表所示:
特征峰 | 保留时间(min) | 峰面积 | 峰面积占比(%) |
1 | 4.801 | 1414991 | 49.9608 |
2 | 6.268 | 1417213 | 50.0392 |
图6b和6c显示制备化合物M32R和化合物M32S时的出峰时间分别为4.805min和6.262min及纯度分别为99.9097%和99.9598%,即得到光学异构体的纯品化合物M32R和M32S。
核磁1H NMR(500MHz,DMSO)δ7.71(dd,J=18.9,7.9Hz,4H),7.29(t,J=7.5Hz,2H),7.03(t,J=7.5Hz,2H),6.80(dt,J=19.7,8.6Hz,18H),6.56(d,J=7.6Hz,2H),6.15(s,2H),3.70(s,12H).
质谱HR-MS(Maldi)计算值C53H42N2O4[M+]:770.31,测试值:770.32。
合成例19手性螺芴异构体M33R&M33S的制备
在氮气氛围下,将2,2'-二溴-9,9'-螺二芴(0.7g,1.48mmol),乙酰丙酮铜(19mg,0.074mmol),叔丁醇钠(0.56g,6.22mmol)和N1,N2-双(4-羟基-2,6-二甲基苯基)草酰胺(L14)(49mg,0.15mmol)在二甲基亚砜和水(10mL v:v=2:1)溶液中充分混合,在120℃加热并搅拌36小时。冷却至室温后,用水淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:99%(0.5g)。
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M33R和M33S。
分析采用0.46cm I.D.×15cm L手性柱,己烷/EtOH=50/50(V/V)为流动相,UV254nm检测,测试结果如图7a-7c所示,图7a显示化合物M33R和化合物M33S的出峰时间分别为2.240min和3.093min,其中,特征峰面积分布数据如下表所示:
特征峰 | 保留时间(min) | 峰面积 | 峰面积占比(%) |
1 | 2.240 | 687185 | 50.118 |
2 | 3.093 | 683951 | 49.882 |
图7b和7c显示制备化合物M33R和化合物M33S时的出峰时间分别为2.246min和3.103min及纯度分别为99.612%和99.456%,即得到光学异构体的纯品化合物M33R和M33S。
核磁1H NMR(500MHz,DMSO)δ9.35(s,1H),7.85(d,J=7.6Hz,1H),7.81(d,J=8.3Hz,1H),7.35(t,J=7.2Hz,1H),7.05(t,J=7.2Hz,1H),6.81(dd,J=8.3,2.2Hz,1H),6.60(d,J=7.5Hz,1H),6.03(d,J=2.0Hz,1H).
质谱HR-MS(Maldi)计算值C25H16O2[M+]:348.12,测试值:348.40。
合成例20手性螺芴异构体M40R&M40S的制备
在氢气氛围下,将化合物M26(0.7g,0.8mmol),钯碳,在氘水溶液中充分混合,在110℃加热并搅拌24小时。冷却至室温后,用饱和氯化铵溶液淬灭该反应。将水层用乙酸乙酯萃取三次,并将合并的有机相用饱和氯化钠水溶液洗涤。有机相用无水硫酸钠干燥后,减压蒸发溶剂至干,所得产物通过硅胶柱色谱进一步纯化,用石油醚/乙酸乙酯(10:1,v/v)作为洗脱剂。得到纯产物,为白色固体。产率:78%(0.54g)
采用HPLC法,使用的制备设备和手性柱对手性异构体分离,收集其相应组分。旋转蒸发除去溶剂,得到光学异构体的纯品化合物M40R和M40S。
质谱HR-MS(Maldi)计算值C65H30D18O2[M+]:878.48,测试值:848.48。
实施例1手性光学膜的制备
以1,1,2,2-四苯乙烯为发光掺杂材料,化合物M16R和M16S为手性源材料,分别配制成20mg/mL的氯仿溶液。
旋涂法:分别将上述两种溶液在氮气氛围下,以转速为800r/min、加速度为500r/min、时间为45秒的匀胶机,滴液量为25微升/次,分三次旋涂在20mm×15mm石英片上。台阶仪测得膜厚约为200nm。
测试例1手性光学膜光至发光测试
通过SHIMADZU(岛津)公司的型号为UV-1750的紫外可见吸收仪和HITACHI(日立)公司生产的型号为F-4600的荧光光谱仪对实施例1得到的手性光学膜进行测试,图8和图9分别为M16R和M16S的紫外可见吸收光谱图和发光光谱图。根据吸收光谱图可以知道,由于1,1,2,2-四苯乙烯的苯基π-π*跃迁在波长为310nm-350nm处有强烈的吸收带。
在320nm激发下,M16R和M16S的发光波长均在450nm左右,与消旋的化合物M16发光光谱一致,可以说明经过手性拆分后材料的结构并没有发生变化,因此完全可以保持消旋体材料的光电性能。
测试例2手性光学膜微观取向
在尼康显微镜(型号:LV100ND)下观察实施例1得到的手性光学膜的形貌,结果如图10a和图10b所示,从图10a中可以看出晶体呈规律性的向左旋转排列附图,这充分说明手性旋螺芴分子可以诱导出手性排列的微结构,由点及线,再由线到面,最终形成圆偏振光发光(CPL)活性高的功能层,且图10b中显示出现四苯基乙烯(TPE)结晶。
测试例3手性光学膜圆偏振光学效应测试
针对实施例1得到的手性光学膜,使用圆偏振荧光光谱仪CPL-300进行圆偏振光测试,激发光源为320nm,检测范围是370nm-700nm。结果如图11a-11d和图12a-12c所示,由图11a-11c可知,M16R和M16S、M31R和M31S、M40R和M40S均在450nm处有明显的圆偏振发光,且如图11d所示,化合物M16R对于左偏振光(IL)和右偏振光(IR)表现出了明显的差异。由图12a-12c可知,不对称因子g值高达10-2(M16R和M16S),该结果证明这种手性螺芴异构体及其衍生物可以获得明显的圆偏振光并且不对称因子g值比常规的要高出一个数量级。
实施例2至实施例19与实施例1的区别仅在于,将化合物16R和16S替换为上述合成例合成得到的其他化合物,具体详见表1。
表1
手性源材料 | 不对称因子g值 | |
实施例2 | 化合物M1R和M1S | 0.037 |
实施例3 | 化合物M2R和M2S | 0.02 |
实施例4 | 化合物M3R和M3S | 0.03 |
实施例5 | 化合物M4R和M4S | 0.015 |
实施例6 | 化合物M5R和M5S | 0.036 |
实施例7 | 化合物M6R和M6S | 0.035 |
实施例8 | 化合物M8R和M8S | 0.08 |
实施例9 | 化合物M10R和M10S | 0.014 |
实施例10 | 化合物M17R和M17S | 0.02 |
实施例11 | 化合物M18R和M18S | 0.04 |
实施例12 | 化合物M19R和M19S | 0.013 |
实施例13 | 化合物M21R和M21S | 0.058 |
实施例14 | 化合物M22R和M22S | 0.015 |
实施例15 | 化合物M25R和M25S | 0.036 |
实施例16 | 化合物M26R和M26S | 0.045 |
实施例17 | 化合物M31R和M31S | 0.07 |
实施例18 | 化合物M32R和M32S | 0.02 |
实施例19 | 化合物M33R和M33S | 0.014 |
实施例20 | 化合物M40R和M40S | 0.08 |
由表1可知,包含上述异构体的手性光学膜均能够产生圆偏振光,由于手性光学膜是圆偏振光器件中的关键组件,将其用于器件中,同样能够使器件稠发射圆偏振光。
实施例20钙钛矿器件制备及发光性能测试
本实施例提供一种底发光的钙钛矿红外器件(结构如图14所示),在器件中钙钛矿材料(FAPbI3)作为发光层,聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)作为空穴注入层,CsF作为电子注入层,1,3,5-三(3-(3-吡啶基)苯基)苯(TmPyPB)作为电子传输层,三氧化钼作为电子阻挡层,金属电极为铝(Al)阴极,氧化铟锡(ITO)为透明阳极,利用消旋的化合物M16作为空穴传输层材料。
利用EQE测试系统对得到的钙钛矿器件在不同电压下进行测试,测试结果如图15a和15b所示,其中,图15a为钙钛矿发光器件的外量子效率图,图15b为钙钛矿发光器件的电致发光光谱图,结果显示该器件发光波长为788nm,属于近红外区发光,器件的外量子效率接近7%,未来在材料和器件均加以优化之后有望实现10%以上的外量子效率。
实施例21有机电致发光(OLED)器件制备及发光性能
本实施例提供一种OLED器件,利用化合物31R作为红光发光掺杂材料用在发光层中,器件通过旋涂法制备,结构为铟锡氧化物(ITO)/聚苯乙烯磺酸(PEDOT:PSS)(45nm)/消旋化合物M31:发光材料(50:50,w/w,40nm)/PO-T2T(45nm)/氟化锂(LiF)(1nm)/铝(Al)(100nm)。PO-T2T代表2,4,6-三[3-(二苯基膦氧基)苯基]-1,3,5-三唑),w/w代表质量比。
利用QE63PRO SpectramScan光谱仪对得到的OLED器件进行测试,测试结果如图16a和16b所示,其中,图16a为OLED发光器件光致发光光谱图,图16b为OLED发光器件发光亮度-电压图,结果显示获得了比较好的发光效果,红光发光波长在633nm,器件的启动电压小于3V,这说明这类材料可以制成高效稳定的发光器件。
实施例22
与实施例21的区别仅在于,将化合物31R替换为消旋的化合物31,器测试结果如图17a-17e所示,其中图17a为OLED发光器件光致发光光谱图,17b为OLED发光器件外量子效率与电流强度图,17c为OLED发光器件发光亮度-电压图,17d为OLED发光器件圆偏振光光谱图,17e为OLED发光器件不对称因子变化图。结果显示获得了比较好的发光效果,与消旋化合物相同红光发光波长在633nm,外量子效率稳定在25%,有明显的圆偏振光,不对称因子可以达到10-2,这说明这类材料可以制成高效稳定的圆偏振发光器件。
申请人声明,本发明通过上述合成例来说明本发明的详细工艺设备和工艺流程,但本发明并不局限于上述详细工艺设备和工艺流程,即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述手性螺芴异构体包括式I中所示的异构体R和异构体S;
式I中,所述m和n各自独立地为0~4的整数,且m和n不同时为0;
式I中,所述A和B各自独立地选自氢、氘、氚、氟、18F同位素、氯、溴、碘、氰基、取代或未取代的C1~C12烷基、取代或未取代的C1~C12烯基、取代或未取代的C1~C12炔基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基、取代或未取代的羟基、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基、氨基胺基、C1~C12烷基取代的氨基、取代或未取代的C12~C30芳胺基、取代或未取代的巯基、取代或未取代的硅基、磷酸酯基、磺酰基中的任意一种,且A和B为不同的基团;
当上述基团存在取代基时,所述取代基选自氘、氚、氟、氯、溴、碘、氰基、羟基、氨基、C1~C12烷基、C1~C12烷氧基、C6~C30芳基、C3~C30杂芳基、C6~C30芳氧基、C12~C30芳胺基中的任意一种或至少两种组合;
其中,虚线代表镜面。
2.根据权利要求1所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述m和n各自独立地为0或1,且m和n不同时为0。
4.根据权利要求1~3中任一项所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述A和B各自独立地选自C1~C12氘代烷基、C6~C30氘代芳基、C1~C12氘代烷氧基、C6~C30氘代芳氧基、C6~C30氘代芳胺基、C1~C12烷氘代烷基取代的氨基、C1~C12烷氘代烷基取代的巯基、C6~C30氘代芳基取代的巯基、C1~C12氘代烷基取代的硅基、C1~C12氘代烷氧基取代的硅基、C6~C30氘代芳基取代的硅基、氘代有机金属取代基、氘代膦基、氘代磷酸酯基、氘代磺酰基中的任意一种。
5.根据权利要求1~3中任一项所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述A取代在2位;
优选地,所述A选自氢原子、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基和取代或未取代的C12~C30芳胺基中的任意一种;
优选地,所述A取代在2位,且所述A选自氢原子、取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳氧基和取代或未取代的C12~C30芳胺基中的任意一种。
6.根据权利要求1~3中任一项所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述B取代在2'位;
优选地,所述B选自氢原子、氰基和氰基取代的C6~C30芳基中的任意一种;
优选地,所述B取代在2'位,且B选自氢原子、氰基和氰基取代的C6~C30芳基中的任意一种。
7.根据权利要求1所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述手性螺芴异构体包括式Ⅲa至式Ⅲd中所示的异构体R和异构体S;
所述FG选自取代或未取代的C1~C12烷氧基、取代或未取代的C6~C30芳基中的任意一种;
所述WFG选自氟、氰基,取代或未取代的吡啶基、取代或未取代的二嗪基、取代或未取代的三嗪基、取代或未取代的咪唑基、取代或未取代的吡唑基、取代或未取代的三氮唑基、取代或未取代的砜基中任意一种;
所述Ar1和Ar2各自独立地选自取代或未取代的C6~C30芳基;
所述π选自取代或未取代的亚乙烯基、取代或未取代的亚乙炔基、取代或未取代的苯基、取代或未取代的C3~C30氮杂芳基、取代或未取代的C10~C30稠环芳基中的任意一种;
其中,虚线代表镜面。
9.根据权利要求1~8中任一项所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述具备手性关联功能的电子元器件包括圆偏振光器件;
优选地,所述具备手性关联功能的电子元器件包括圆偏振光电致发光器件、手性分子开关器、手性场效应晶体管器件和手性分子探针器件中的任意一种;
优选地,所述圆偏振光器件中含有手性光学膜,所述手性光学膜中含有所述手性螺芴异构体。
10.根据权利要求9所述的手性螺芴异构体在具备手性关联功能的电子元器件中的应用,其特征在于,所述圆偏振光器件中含有有机功能层,所述有机功能层中含有所述手性螺芴异构体;
优选地,所述有机功能层包括发光层、电荷传输层、电荷注入层和光改性层中的任意一种或至少两种组合;
优选地,所述发光层中含有所述手性螺芴异构体;
优选地,所述手性螺芴异构体作为发光层的发光材料、主体材料或客体材料。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112920059A (zh) * | 2019-12-06 | 2021-06-08 | 常州强力昱镭光电材料有限公司 | 多取代螺二芴化合物、空穴传输材料组合物及光电器件 |
-
2019
- 2019-11-13 CN CN201911105496.8A patent/CN110790629B/zh active Active
Non-Patent Citations (7)
Title |
---|
CYRIL PORIEL,ET AL.,: ""New generations of spirobifluorene regioisomers for organic electronics: tuning electronic properties with the substitution pattern"", 《CHEM. COMMUN.,》 * |
KO TAKASE,ET AL.,: ""[1]Benzothiophene-Fused Chiral Spiro Polycyclic Aromatic Compounds: Optical Resolution, Functionalization, and Optical Properties"", 《J. ORG. CHEM.》 * |
KO TAKASE,ET AL.,: ""Circularly Polarized Luminescence from Chiral Spiro Molecules:", 《ORG. LETT.》 * |
KOJI MIK, ET AL.,: ""Near-Infrared Circularly Polarized Luminescence through Intramolecular Excimer Formation of Oligo(p- phenyleneethynylene)-Based Double Helicates"", 《CHEM. EUR. J.》 * |
MASAHIRO KUBO ET AL.,: ""Solvent-sensitive circularly polarized luminescent compounds bearing a 9,9 ’ -spirobi[ fluorene] skeleton"", 《ORG. BIOMOL. CHEM.,》 * |
李庆祥等: ""诱导手性圆偏振发光材料的研究进展"", 《功能高分子学报》 * |
李猛等: ""手性有机小分子圆偏振发光的研究进展 "", 《ACTA CHIM. SINICA 》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112920059A (zh) * | 2019-12-06 | 2021-06-08 | 常州强力昱镭光电材料有限公司 | 多取代螺二芴化合物、空穴传输材料组合物及光电器件 |
WO2021109819A1 (zh) * | 2019-12-06 | 2021-06-10 | 常州强力昱镭光电材料有限公司 | 多取代螺二芴化合物、空穴传输材料组合物及光电器件 |
CN112920059B (zh) * | 2019-12-06 | 2023-09-05 | 常州强力昱镭光电材料有限公司 | 多取代螺二芴化合物、空穴传输材料组合物及光电器件 |
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