CN113024482B - 一种芳基酮类化合物及其制备方法和应用 - Google Patents

一种芳基酮类化合物及其制备方法和应用 Download PDF

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CN113024482B
CN113024482B CN202110261096.7A CN202110261096A CN113024482B CN 113024482 B CN113024482 B CN 113024482B CN 202110261096 A CN202110261096 A CN 202110261096A CN 113024482 B CN113024482 B CN 113024482B
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ketone compound
aryl ketone
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binaphthol
carbonate
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霍延平
陈丽芬
邓明佳
穆英啸
罗许伟
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Guangdong University of Technology
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Abstract

本发明公开了一种芳基酮类化合物及其制备方法和应用。所述化合物以手性基团联二萘酚作为修饰基团，使基于该基团的发光分子具备圆偏振发光性质；二苯甲酮为电子受体(A)，通过向其引入合适的电子给体(D)构成具有D‑A结构的电荷转移态的化合物。具有较高的发光强度，提高了光致发光量子产率，所述光致发光量子产率最小值为92％。能够应用于防伪标识、发光器件或生物成像方面。

Description

一种芳基酮类化合物及其制备方法和应用
技术领域
本发明涉及有机发光材料技术领域，更具体地，涉及一种芳基酮类化合物及其制备方法和应用。
背景技术
手性分子是结构镜像对称，但不完全重合。目前，手性分子已广泛用于不对称合成，手性识别，对映体分离等各个领域。特别是，显示偏振光的材料在液晶显示面板，3D成像系统，信息存储，非线性光学，自旋电子器件和生物探针等领域具有潜在的应用背景。
圆偏振发光(CPL)是指由激发态手性发光体发出的左旋和右旋圆偏振光的不同发射。根据相关研究，圆偏振光可改善图像对比度的质量并保护视力健康。通常，由有机发光二极管(OLED)制造的平板显示器需要偏光片和四分之一波片来降低周围环境光的反射率以获得较高的图像，然而在从非偏振光到平面偏振光的过渡过程中会引起能量损耗。因此，需要开发一系列能够直接产生包含右旋和左旋圆偏振光的圆偏振发光的手性发光材料。
近几年的研究发现手性聚合物和手性过渡金属配合物可以使圆偏振有机发光二极管(CP-OLED)具有高的圆偏振电致发光性能，然而其效率往往会随着亮度的增加而降低。其中手性有机小分子具有分子设计选择范围广、可修饰性强、荧光量子产率高，且相对分子质量小以及可制备电致发光器件等优点，可为CP-OLED提供可调谐的圆偏振电致发光，且具有低效率滚降的优点，是裸眼、高效3D显示设备等设备用电致发光材料的有力竞争者，这是其他类型的圆偏振发光材料所难以比拟的。然而，目前所报道的应用于CP-OLED的圆偏振发光材料难以实现高的光致发光量子产率。
中国专利(CN110669065A)公开了一种基于轴手性联二萘酚-氟硼二吡咯配合物及其制备方法，所述化合物的量子产率最大值仅有81％，因此，急需提高光致发光量子产率，使得圆偏振发光材料得以应用。
发明内容
本发明为克服光致发光量子产率低的缺陷，提供一种芳基酮类化合物。
本发明另一目的在于提供所述芳基酮类化合物的制备方法。
本发明另一目的在于提供所述芳基酮类化合物的应用。
为实现上述目的，本发明采用的技术方案是：
一种芳基酮类化合物，具有如式(Ⅰ)所示的分子结构：
Figure BDA0002970011020000021
其中R1、R2为给体基团，独立的选自如下结构式：
Figure BDA0002970011020000022
Figure BDA0002970011020000023
中的一种，所述R选自H、t-Bu。
本发明以手性基团联二萘酚作为修饰基团，使基于该基团的发光分子具备圆偏振发光性质；二苯甲酮为电子受体(A)，通过向其引入合适的电子给体(D)构成具有D-A结构的电荷转移态的圆偏振有机发光材料。二苯甲酮具有一个大的扭曲角的吸电子性高的羰基，且具备有效的系间窜越，因此，通过合理的分子设计有利于使D-A分子形成大的扭转以减少前线分子轨道的重叠，从而减小了单-三线态能级差，有效促进了反向系间窜越进程，提高了热激活延迟荧光的性能。此外，羰基能引发分子产生振动，进而产生聚集诱导发光(AIE)效应，可以有效地抑制激子湮灭，使分子在高浓度聚集态下比低浓度下有更强的荧光发射，从而具有较高的发光强度，提高了光致发光量子产率。
优选地，所述R1、R2独立的选自如下结构式：
Figure BDA0002970011020000031
Figure BDA0002970011020000032
中的一种。
所述芳基酮类化合物的结构式如下所示：
Figure BDA0002970011020000033
Figure BDA0002970011020000041
本发明还提供所述芳基酮类化合物的制备方法，包括以下步骤：
S1.将联二萘酚、碳酸盐、4,4-二氟二苯甲酮溶于有机溶剂中，经过加热反应及后处理，得到中间体1。
S2.将步骤S1的产物1与碱性盐，给体基团共溶于有机溶剂中，经过加热反应及后处理，得到芳基酮类化合物。
优选地，所述步骤S1中碳酸盐为碳酸铯或碳酸钾中的一种或两种。
优选地，所述步骤S1和步骤S2的有机溶剂为N,N-二甲基甲酰胺或二甲基亚砜中一种。
优选地，步骤S1中所述联二萘酚、碳酸盐、4,4-二氟二苯甲酮的摩尔比为1：(2～6)：(2～3)。
优选地，步骤S1中所述加热反应的温度为75～100℃，反应时间为8～16h。
优选地，步骤S2中所述中间体1，碱性盐，给体基团的摩尔比为1：(2～6)：(2～3)。
优选地，步骤S2中所述加热反应的温度为90～130℃，反应时间为10～16h。
所述联二萘酚为左旋联二萘酚或者右旋联二萘酚。
所述芳基酮类化合物在防伪标识、发光器件或生物成像方面的应用。
与现有技术相比，本发明的有益效果是：
本发明提供了一种芳基酮类化合物，所述化合物以手性基团联二萘酚作为修饰基团，使基于该基团的发光分子具备圆偏振发光性质；二苯甲酮为电子受体(A)，通过向其引入合适的电子给体(D)构成具有D-A结构的电荷转移态的圆偏振有机发光材料。具有较高的发光强度，提高了光致发光量子产率，所述光致发光量子产率至少为92％。能够应用于防伪标识、发光器件或生物成像方面。
附图说明
图1为本发明实施例1制备的化合物A1的核磁共振氢谱图；
图2为本发明实施例1制备的化合物A1的质谱图；
图3为本发明实施例1制备的化合物A1在1.0×10-5M的四氢呋喃溶液中的紫外吸收光谱；
图4为本发明实施例1制备的化合物A1在薄膜状态下的荧光光谱和磷光光谱；
图5为本发明实施例1制备的化合物A1的四氢呋喃溶液(1.0×10-5M)中的圆二色谱；
图6为本发明实施例1制备的化合物A1薄膜状态下的圆二色谱；
图7为本发明实施例2制备的化合物A2的核磁共振氢谱图；
图8为本发明实施例3制备的化合物A3的核磁共振氢谱图；
图9为本发明实施例4制备的化合物A4的核磁共振氢谱图。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例中的原料均可通过市售得到；
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
本实施例提供一种芳基酮类化合物，结构式如A1所示，
Figure BDA0002970011020000061
该化合物的制备方法如下：
Figure BDA0002970011020000062
S1.在100mL圆底烧瓶中按摩尔比1:2:1称取联二萘酚、碳酸铯、4,4-二氟二苯甲酮溶于N,N-二甲基甲酰胺。在氮气保护的条件下，将上述反应物加热至100℃并反应10h。待反应结束后，将反应液冷却至室温，用乙酸乙酯和饱和食盐水萃取反应液3次。取有机相，减压蒸发乙酸乙酯后得到粗产物。再通过硅胶柱色谱层析法，以乙酸乙酯/正己烷为洗脱剂，进行分离纯化，得到中间体1，所述中间体1的结构式如下所示
Figure BDA0002970011020000063
S2.在100mL圆底烧瓶中按摩尔比1:2:2称取步骤S1的产物1，碱性盐，给体基团共溶于N,N-二甲基甲酰胺。在氮气保护的条件下，将上述反应物加热至110℃并反应12h。待反应结束后，将反应液冷却至室温，用乙酸乙酯和饱和食盐水萃取反应液3次。取有机相，减压蒸发乙酸乙酯后得到粗产物。再通过硅胶柱色谱层析法，以乙酸乙酯/正己烷为洗脱剂，进行分离纯化，得到芳基酮类圆偏振热激活延迟荧光材料A1。
实施例2
本实施例提供一种芳基酮类化合物，其制备
Figure BDA0002970011020000071
例1相同，其区别在于，与实施例1不同的是，R1和R2的基团都为。。得到芳基酮类化合物A2，A2的结构式如下所示。
Figure BDA0002970011020000072
实施例3
本实施例提供一种芳基酮类化合物，其制备方法与实施例1相同，其区别在于，与实施例1不同的是，R1和R2的基团都为
Figure BDA0002970011020000073
得到芳基酮类化合物A3，A3的结构式如下所示。
Figure BDA0002970011020000074
实施例4
本实施例提供一种芳基酮类化合物，其制备方法如下：
Figure BDA0002970011020000075
S1.在100mL圆底烧瓶中按摩尔比1:2:1称取联二萘酚、碳酸铯、4-氟，4-溴-二苯甲酮溶于N,N-二甲基甲酰胺。在氮气保护的条件下，将上述反应物加热至100℃并反应10h。待反应结束后，将反应液冷却至室温，用乙酸乙酯和饱和食盐水萃取反应液3次。取有机相，减压蒸发乙酸乙酯后得到粗产物。再通过硅胶柱色谱层析法，以乙酸乙酯/正己烷为洗脱剂，进行分离纯化，得到中间体2，中间体2的结构式如下所示，
Figure BDA0002970011020000081
S2.在100mL圆底烧瓶中按摩尔比1:2:2称取步骤S1的产物1，碱性盐，给体基团共溶于乙醇/甲苯/水(比例为2：2：1)的混合液中。在氮气保护的条件下，将上述反应物加热至90℃并反应6h。待反应结束后，将反应液冷却至室温，用乙酸乙酯和饱和食盐水萃取反应液3次。取有机相，减压蒸发乙酸乙酯后得到粗产物。再通过硅胶柱色谱层析法，以乙酸乙酯/正己烷为洗脱剂，进行分离纯化，得到芳基酮类化合物A4，A4的结构式如下所示。
Figure BDA0002970011020000082
实施例5
本实施例提供一种芳基酮类化合物，其制备方法与实施例1相同，其区别在于，与实施例1不同的是，R1和R2的基团都为
Figure BDA0002970011020000083
得到芳基酮类化合物A5，A5的结构式如下所示。
Figure BDA0002970011020000084
实施例6
本实施例提供一种芳基酮类化合物，其制备方法与实施例4相同，其区别在于，与实施例4不同的是，R1和R2的基团都为
Figure BDA0002970011020000085
得到芳基酮类化合物A6，A6的结构式如下所示。
Figure BDA0002970011020000091
性能测试
选取实施例1制备的芳基酮类化合物进行性能测试。
测试方法如下：
化合物结构检测：使用布鲁克400MHz超导核磁共振仪，溶剂为氘代DMSO；
质谱检测：将实施例1制得的A1溶于乙腈，配成浓度为1mg/mL的溶液，采用液质联用仪LCMS-2020，进行质谱测试；
紫外吸收光谱检测：使用岛津紫外可见分光光度计UV-2700，扫描范围是250～700nm；
发射光谱检测：使用稳态/瞬态荧光光谱仪(FLS980)，激发波长为350nm，在氮气保护下，测试温度为77K，300K；
圆二色谱检测：使用Chirascan圆二色光谱仪，扫描范围是200-800nm。
量子产率测试：使用稳态/瞬态荧光光谱仪(FLS980)，测试方法：首先，参数设置，用产物的的最佳激发波长330nm激发，空白石英片做参比，保持激发与发射的狭缝宽度一致。
测试结果如下：
实施例1制备的芳基酮类化合物A1的分子氢谱如图1所示。可以看出：1H NMR(400MHz,DMSO)δ8.16(d,J＝9.0Hz,2H),8.07(d,J＝8.2Hz,2H),7.85(d,J＝8.3Hz,4H),7.67(d,J＝8.7Hz,4H),7.58–7.35(m,8H),7.17(d,J＝8.5Hz,2H),6.94(d,J＝8.7Hz,4H),6.81–6.60(m,10H),5.99–5.89(m,4H)，分子氢谱波峰能与目标产物一一对应，数量合理；从质谱图(图2)中可以看到，图中相对分子质量为1009.32，减去一个H，与所合成的A1的相对分子质量一致。结合以上核磁和质谱的结果可知，实施例1制得的产物为A1。
实施例2制备的芳基酮类化合物A2的分子氢谱如图7所示。可以看出：1H NMR(600MHz,DMSO)δ8.13(d,J＝9.0Hz,2H),8.04(d,J＝8.2Hz,2H),7.66(t,J＝5.6Hz,4H),7.58(d,J＝11.6Hz,4H),7.49(t,J＝7.5Hz,2H),7.42–7.36(m,8H),7.18(dddd,J＝15.1,13.9,5.6,3.9Hz,15H),6.92(ddd,J＝32.1,7.5,1.5Hz,8H).分子氢谱波峰能与目标产物一一对应，数量合理；
实施例3制备的芳基酮类化合物A3的分子氢谱如图8所示。可以看出：1H NMR(400MHz,DMSO)δ8.16(d,J＝9.0Hz,2H),8.07(d,J＝8.1Hz,2H),7.88(d,J＝8.4Hz,4H),7.69(s,4H),7.57–7.34(m,12H),7.18(d,J＝8.5Hz,2H),7.07–6.85(m,12H),6.21(dd,J＝8.0,1.1Hz,4H),1.61(s,12H).分子氢谱波峰能与目标产物一一对应，数量合理；
实施例4制备的芳基酮类化合物A4的分子氢谱如图9所示。可以看出：1H NMR(600MHz,DMSO)δ8.17(d,J＝9.0Hz,2H),8.08(d,J＝8.2Hz,2H),7.94(s,2H),7.87–7.81(m,8H),7.71–7.61(m,11H),7.57–7.51(m,4H),7.46(d,J＝9.0Hz,2H),7.42–7.33(m,6H),7.19(d,J＝8.5Hz,2H),6.92(s,4H),1.48(s,6H).分子氢谱波峰能与目标产物一一对应，数量合理；
采用岛津紫外可见光分光光度计UV-2700，将实施例1制得的A1，A2，A3，A4溶于四氢呋喃(THF)溶液中配成1×10-3mol/L的母液，稀释成1×10-5mol/L进行测试。
从图3中看出，四个分子的主要吸收峰位置为290nm左右。
使用该发光材料制备掺杂薄膜，制备方法如下：
称量一定质量样品，使用可溶解的溶剂进行配样，利用旋涂蒸发溶剂方法即可制备薄膜。
对该发光材料薄膜进行发光性能测试，结果如图4所示。图4为发光材料旋涂薄膜在氮气保护下归一化温度依赖稳态光谱。从图4中看出，A1的发射波长为560nm，荧光光谱和磷光光谱的起峰位置分别为474nm，491nm。由此计算可得的单-三线态能隙为0.09eV，远远小于0.3eV，可实现更高的反向系间窜越速率和更高的能量利用率。可证明A1具有热激活延迟荧光性能。
从图5、图6看出，(S)-A1与(R)-A1在溶液和薄膜状态下均表现出对于左旋或右旋圆偏振光的选择性吸收，这表明将基于手性联二萘酚的芳基酮发光材料可以连接不同电子给体获得多种圆偏振发光材料。
表1实施例的数据
Figure BDA0002970011020000101
Figure BDA0002970011020000111
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (9)

1.一种芳基酮类化合物，其特征在于，具有如式A1～A23所示的分子结构：
Figure FDA0003302506200000011
Figure FDA0003302506200000021
。
2.根据权利要求1所述芳基酮类化合物的制备方法，其特征在于，包括以下步骤：
S1.将联二萘酚、碳酸盐、4,4-二氟二苯甲酮溶于有机溶剂中，经过加热反应及后处理，得到中间体1；
S2.将步骤S1的中间体1与碱性盐，给体基团共溶于有机溶剂中，经过加热反应及后处理，得到芳基酮类化合物。
3.根据权利要求2所述制备方法，其特征在于，所述步骤S1中碳酸盐为碳酸铯或碳酸钾中的一种。
4.根据权利要求2所述制备方法，其特征在于，所述步骤S1和步骤S2的有机溶剂为N,N-二甲基甲酰胺或二甲基亚砜中一种。
5.根据权利要求2所述制备方法，其特征在于，步骤S1中所述联二萘酚、碳酸盐、4,4-二氟二苯甲酮的摩尔比为1：(2～6)：(2～3)。
6.根据权利要求2所述制备方法，其特征在于，步骤S1中所述加热反应的温度为75～100℃，反应时间为8～16h。
7.根据权利要求2所述制备方法，其特征在于，步骤S2中所述中间体1、碱性盐和给体基团的摩尔比为1：(2～6)：(2～3)。
8.根据权利要求2所述制备方法，其特征在于，步骤S2中所述加热反应的温度为90～130℃，反应时间为10～16h。
9.权利要求1所述芳基酮类化合物在防伪标识、发光器件中的应用。
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