CN108373922B - 一种含芘的手性发光液晶化合物及其制备方法 - Google Patents
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Abstract
本发明提供了一种含芘的手性发光液晶化合物及其制备方法,所述化合物,其结构通式为(C40H71NO2Tn)4C16H6(SO3)4,式中:Tn为烷基碳链‑CnH2n+1,其中n=1,2,6,10,12或14。其制备步骤:首先,采用11‑溴十一酸胆固醇酯与三级胺进行季铵化反应,得到手性阳离子表面活性剂;然后,利用上述手性阳离子表面活性剂与1,3,6,8‑芘四磺酸四钠盐进行离子自组装,得到含芘的手性发光液晶化合物。本发明操作简单、反应时间短、产率高、易于工业化生产,该含芘的化合物不仅表现出手性液晶性,而且具有强烈的荧光,有望在偏振发光材料、生物传感器、液晶显示器等方面得到广泛应用。
Description
技术领域
本发明涉及液晶材料领域,具体涉及一种含芘的手性发光液晶化合物及其制备方法。
背景技术
手性液晶是一类重要的功能材料,因分子中手性中心的存在而具有旋光性、选择性反射、圆二色性、热致变色等光学性能。因手性液晶本身并不发光,手性液晶材料在显示应用时所需的背光源、滤色膜等光学器件很大程度上降低了显示器的亮度、对比度和能效。手性发光液晶材料同时具有手性液晶性和发光性,在取向排列时会发出圆偏振光,应用时将大大简化器件结构、增加亮度、提高能效,将使液晶显示变得更节能、更轻薄。由于将发光基团引入手性液晶分子中难以保持其液晶性,另外很多发光材料在聚集态时的发光会大大减弱甚至淬灭,所以设计与合成具有发光特性的手性液晶材料仍面临着诸多挑战。
芘是一类良好的蓝色发光材料,具有独特的荧光性能,比如量子产率高、荧光寿命长、对光稳定、对微环境改变反应灵敏等,这些特性使芘及其衍生物在发光材料、荧光探针、荧光染料等方面具有广泛应用。考虑到芘的强功能特性,将芘引入手性液晶中不仅是构筑多功能液晶材料的有效方法,而且可利用液晶的响应特性来可逆地调控芘的发光性能,这为设计与开发基于芘的偏振发光材料、生物传感器、液晶显示器等具有重要的指导意义。
多个研究团队都在从事芘类非手性液晶材料的开发,Hee-Tae Jung等人将含氟碳链修饰的苯甲酸与含羟基的芘进行酯化反应,制得含芘的非手性发光液晶材料(J.Phys.Chem.B,2006,110,20836-20842)。Raymond Ziessel等人将三(十六烷氧基)修饰的炔类中间体分别共价修饰芘的1,6或1,3,6,8位上,得到双对称或四对称的芘类非手性液晶材料(J.Am.Chem.Soc.2009,131,18177–18185)。Ronan Lefort等人将通过酯化反应将正辛醇共价修饰到芘四苯甲酸的外围,并对化合物组装成的盘状液晶进行了分子动力学研究(RSC Adv.2014,4,59358–59369)。Kato等人将含长烷基链的谷氨酸衍生物共价修饰到芘上,首次成功制得了六方柱状结构的手性液晶材料(Org.Lett.,2006,8,2463-2466)。但到目前为止,所报道过的芘类手性液晶材料虽有液晶性但其液晶转变温度高且区间窄;其制备方法都是通过共价相互作用合成的。手性共价合成方法具有繁琐、耗时、成本高及分离提纯困难等弊端,因此开发一种制备芘类手性发光液晶材料的简单方法十分必要。
发明内容
本发明的目的是提供一种含芘的手性发光液晶化合物及其制备方法,该化合物能在室温下具有手性液晶性且温度区间宽,并具有较强的荧光;该方法简单易行,反应设备简单,操作条件温和,产物易分离纯化,易于实现工业化生产。
本发明提供的一种含芘的手性发光液晶化合物,其基本结构由含胆固醇基团的手性季铵盐型阳离子及1,3,6,8-芘四磺酸阴离子构成,其通式为(C40H71NO2Tn)4C16H6(SO3)4,式中:Tn为烷基碳链-CnH2n+1,其中n=1,2,6,10,12或14,结构式为:
本发明首先采用11-溴十一酸胆固醇酯(参考文献Chem.Asian J.2016,11(14),2001–2005合成)与三级胺进行季铵化反应,得到手性阳离子表面活性剂;然后,利用上述手性阳离子表面活性剂与1,3,6,8-芘四磺酸四钠盐进行离子自组装,得到含芘的手性发光液晶化合物。
反应式为:
本发明手性发光液晶化合物的制备方法,包括以下步骤:
(1)手性阳离子表面活性剂的合成
将11-溴十一酸胆固醇酯加热溶解在丙酮中,保持浓度为5-8mg/mL;再加入三级胺,使三级胺与卤代脂肪酸胆固醇酯的摩尔比为6-10:1;在氮气保护下回流反应24-48h;旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到含胆固醇基团的手性阳离子表面活性剂;
(2)手性发光液晶化合物的合成
将手性阳离子表面活性剂溶于体积比为0.8-1.2:1的甲醇/水混合溶剂中,保持其浓度为10-25mg/mL;将1,3,6,8-芘四磺酸四钠盐溶于另一体积比为0.8-1.2:1的甲醇/水的混合溶剂中,保持其浓度为2-6mg/mL;控制手性阳离子表面活性剂与1,3,6,8-芘四磺酸四钠盐的摩尔比为3-5:1,在40-70℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到表面活性剂溶液中;继续搅拌1-3h后离心分离得到沉淀;再用甲醇/水的混合溶剂洗涤沉淀3-5次,离心分离得到沉淀;真空干燥得到含芘的手性发光液晶化合物。
步骤(1)中所述的三级胺为三甲胺、N,N-二甲基乙胺、N,N-二甲基己胺、N,N-二甲基癸胺、N,N-二甲基十二烷基胺或N,N-二甲基十四烷基胺。
与现有技术相比本发明的有益效果:
(1)本发明利用离子自组装方法,以含胆固醇基团的手性阳离子表面活性剂静电修饰芘得到含芘的手性发光液晶化合物。该化合物不仅在室温下表现出手性液晶性且温度区间宽,并具有较强的荧光。
(2)离子自组装方法具有良好的结构可设计性和功能可调节性,更利于更换其他表面活性剂静电修饰芘以实现具有不同性质的多功能材料。
(3)利用离子自组装方法以非共价相互作用为驱动力构筑含芘的超分子手性材料,克服了手性共价合成方法繁琐、耗时及成本高等弊端。
(4)本发明方法简单易操作,无需复杂的反应设备,操作条件温和,反应时间短,产率高,产物易分离纯化,易于工业化生产。
附图说明
图1:实施例1中所述分子(C40H71NO2T12)4C16H6(SO3)4的红外光谱;
图2:实施例1中所述分子(C40H71NO2T12)4C16H6(SO3)4的核磁共振波谱;
图3:实施例4中所述分子(C40H71NO2T1)4C16H6(SO3)4的红外光谱;
图4:实施例4中所述分子(C40H71NO2T1)4C16H6(SO3)4的核磁共振波谱;
图5:实施例1中所述分子(C40H71NO2T12)4C16H6(SO3)4的偏光显微镜照片;
图6:实施例1中所述分子(C40H71NO2T12)4C16H6(SO3)4的变温X-射线衍射;
图7:实施例4中所述分子(C40H71NO2T1)4C16H6(SO3)4的变温荧光光谱;
具体实施方式
实施例1:(C40H71NO2T12)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在170mL丙酮中,再加入2.69g N,N-二甲基十二烷基胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T12Br,产率为79%。
(2)将1g C40H71NO2T12Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.18g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T12Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1,在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T12Br溶液中。继续搅拌1h后离心分离得到沉淀,再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T12)4C16H6(SO3)4,产率为77%。
图1是(C40H71NO2T12)4C16H6(SO3)4的红外光谱,3466cm-1为O-H反对称伸缩振动;2925和2851cm-1为CH2反对称和对称伸缩振动;1736cm-1为C-O伸缩振动;1467cm-1为CH2剪切振动;740、660和589cm-1为芘的特征吸收振动峰,说明所得化合物中含有表面活性剂和芘。通过对比阳离子表面活性剂C40H71NO2T12Br(A)与芘超分子化合物C40H71NO2T12)4C16H6(SO3)4(B)的核磁共振波谱(见图2),发现静电复合之后(C40H71NO2T12)4C16H6(SO3)4中季铵盐亚甲基、甲基上的氢(c、d)向高场低位移方向移动,表明季铵盐离子基团的静电相互作用发生了变化,静电修饰成功。另外,通过计算(C40H71NO2T12)4C16H6(SO3)4中分别归属于芘上与季铵盐上的氢的比例,得知芘外围修饰有4个表面活性剂分子,说明芘外围的4个抗衡阳离子Na+完全被阳离子表面活性剂所替换,形成了含芘的超分子化合物(C40H71NO2T12)4C16H6(SO3)4。
实施例2:(C40H71NO2T12)4C16H6(SO3)4的合成
(1)控制N,N-二甲基十二烷基胺(2.02g)与11-溴十一酸胆固醇酯(1g)的摩尔比为6:1,其余同实施例1,产率为72%。
(2)控制C40H71NO2T12Br(1g)与1,3,6,8-芘四磺酸四钠盐(0.14g)的摩尔比为5:1,其余同实施例1,产率为74%。
实施例3:(C40H71NO2T12)4C16H6(SO3)4的合成
(1)控制N,N-二甲基十二烷基胺(3.37g)与11-溴十一酸胆固醇酯(1g)的摩尔比为10:1,其余同实施例1,产率为81%。
(2)控制C40H71NO2T12Br(1g)与1,3,6,8-芘四磺酸四钠盐(0.24g)的摩尔比为3:1,其余同实施例1,产率为78%。
实施例4:(C40H71NO2T1)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在160mL丙酮中,再加入2.33g 40%的三甲胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T1Br,产率为81%。
(2)将1g C40H71NO2T1Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.22g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T1Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1。在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T1Br溶液中。继续搅拌1h后离心分离得到沉淀。再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T1)4C16H6(SO3)4,产率为84%。
图3是(C40H71NO2T1)4C16H6(SO3)4的红外光谱,3431cm-1为O-H反对称伸缩振动;2933和2852cm-1为CH2反对称和对称伸缩振动;1731cm-1为C-O伸缩振动;1467cm-1为CH2剪切振动;740、657和592cm-1为芘的特征吸收振动峰,说明所得化合物中既含表面活性剂又含芘。通过对比阳离子表面活性剂C40H71NO2T1Br(A)与芘超分子化合物C40H71NO2T1)4C16H6(SO3)4(B)的核磁共振波谱(见图4),发现静电复合之后(C40H71NO2T1)4C16H6(SO3)4中季铵盐亚甲基、甲基上的氢(c、d)向高场低位移方向移动,表明季铵盐离子基团的静电相互作用发生了变化,静电修饰成功。另外,通过计算(C40H71NO2T1)4C16H6(SO3)4中分别归属于芘上与季铵盐上的氢的比例,得知芘外围修饰有4个表面活性剂分子,说明芘外围的4个抗衡阳离子Na+完全被阳离子表面活性剂所替换,形成了含芘的超分子化合物(C40H71NO2T1)4C16H6(SO3)4。
实施例5:(C40H71NO2T2)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在150mL丙酮中,再加入1.15g N,N-二甲基乙胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T2Br,产率为85%。
(2)将1g C40H71NO2T2Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.22g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T2Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1。在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T2Br溶液中。继续搅拌1h后离心分离得到沉淀。再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T2)4C16H6(SO3)4,产率为82%。
实施例6:(C40H71NO2T6)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在150mL丙酮中,再加入1.63g N,N-二甲基己胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T6Br,产率为80%。
(2)将1g C40H71NO2T6Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.20g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T6Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1。在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T6Br溶液中。继续搅拌1h后离心分离得到沉淀。再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T6)4C16H6(SO3)4,产率为79%。
实施例7:(C40H71NO2T10)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在150mL丙酮中,再加入2.34g N,N-二甲基癸胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T10Br,产率为76%。
(2)将1g C40H71NO2T10Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.19g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T10Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1。在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T10Br溶液中。继续搅拌1h后离心分离得到沉淀。再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T10)4C16H6(SO3)4,产率为78%。
实施例8:(C40H71NO2T14)4C16H6(SO3)4的结构与合成
(1)将1g 11-溴十一酸胆固醇酯加热溶解在150mL丙酮中,再加入3.05g N,N-二甲基十四烷基胺,在氮气保护下回流反应36h,旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到季铵盐型离子化合物C40H71NO2T14Br,产率为75%。
(2)将1g C40H71NO2T14Br溶解在60mL体积比为1:1的甲醇/水混合溶剂中,0.17g1,3,6,8-芘四磺酸四钠盐溶解在另一60mL体积比为1:1的甲醇/水混合溶剂中。控制C40H71NO2T14Br与1,3,6,8-芘四磺酸四钠盐的摩尔比为4:1。在50℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到C40H71NO2T14Br溶液中。继续搅拌1h后离心分离得到沉淀。再用甲醇/水的混合溶剂洗涤沉淀3次,离心分离得到沉淀。真空干燥得到含芘的手性发光液晶化合物(C40H71NO2T14)4C16H6(SO3)4,产率为72%。
实施例9:(C40H71NO2T12)4C16H6(SO3)4的手性液晶性
利用偏光显微镜对(C40H71NO2T12)4C16H6(SO3)4的多畴样品进行液晶织构的观察,取少量研磨均匀的样品置于两层圆形盖玻片夹层中,轻压盖玻片。将上述所制样品置于偏光显微镜的热台中,利用正交偏光观察液晶分子的热致液晶行为。从各向同性态降温至150℃,有典型的游丝织构(见图5)出现,这意味着(C40H71NO2T12)4C16H6(SO3)4组装成了手性液晶相。在从各向同性态第一次降温至152℃时,(C40H71NO2T12)4C16H6(SO3)4的X-射线衍射图谱的小角区出现两个等间距的衍射峰001、002(见图6),表明为层结构,层间距d为3.84nm;广角区在20°处没有出现衍射峰,表明此时烷基链处于无序堆积状态;降温至25℃,层结构保持不变,这说明(C40H71NO2T12)4C16H6(SO3)4是典型的手性室温液晶材料,且液晶区间较宽。X-射线衍射图谱与偏光显微镜表明(C40H71NO2T12)4C16H6(SO3)4的液晶相态为手性近晶A(SmA*)相。
实施例10:(C40H71NO2T1)4C16H6(SO3)4的发光性质
图7是(C40H71NO2T1)4C16H6(SO3)4的变温荧光光谱。在30℃时,在387nm、410nm和432nm出现了较强的特征发射峰,这表明(C40H71NO2T1)4C16H6(SO3)4具有强烈的荧光。芘的光物理性质对其周围的微环境很敏感,芘在不同聚集形态中的光物理性质有着丰富的变化。从变温荧光光谱中可知,芘的荧光强度是随着温度逐渐降低的,这是由于随温度升高,分子间碰撞加剧,荧光淬灭的结果。结果表明,(C40H71NO2T1)4C16H6(SO3)4的光物理性质可通过精确控制温度来调节。
Claims (2)
2.权利要求1所述含芘的手性发光液晶化合物的制备方法,其特征在于包括以下步骤:
(1)手性阳离子表面活性剂的合成
将11-溴十一酸胆固醇酯加热溶解在丙酮中,保持浓度为5-8 mg/mL;再加入三级胺,使三级胺与11-溴十一酸胆固醇酯的摩尔比为6-10 : 1;在氮气保护下回流反应24-48h;旋转蒸发除去溶剂,用氯仿/乙醚重结晶3次,得到含胆固醇基团的手性阳离子表面活性剂;
(2)手性发光液晶化合物的合成
将手性阳离子表面活性剂溶于体积比为0.8-1.2 : 1的甲醇/水混合溶剂中,保持其浓度为10-25 mg/mL;将1,3,6,8-芘四磺酸四钠盐溶于另一体积比为0.8-1.2 : 1的甲醇/水的混合溶剂中,保持其浓度为2-6 mg/mL;控制手性阳离子表面活性剂与1,3,6,8-芘四磺酸四钠盐的摩尔比为3-5 : 1,在40-70℃并剧烈搅拌状态下,将1,3,6,8-芘四磺酸四钠盐溶液加入到表面活性剂溶液中;继续搅拌1-3 h后离心分离得到沉淀;再用甲醇/水的混合溶剂洗涤沉淀3-5次,离心分离得到沉淀,真空干燥得到含芘的手性发光液晶化合物;
步骤(1)中所述的三级胺为三甲胺、N,N-二甲基乙胺、N,N-二甲基己胺、N,N-二甲基癸胺、N,N-二甲基十二烷基胺或N,N-二甲基十四烷基胺。
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WO2015068858A1 (en) * | 2013-11-06 | 2015-05-14 | Kyushu University, National University Corporation | Solvent-free photon upconversion system |
CN104232077A (zh) * | 2014-08-28 | 2014-12-24 | 陕西师范大学 | 基于胆固醇修饰的单芘荧光探针及其合成方法和应用 |
CN106170474A (zh) * | 2014-09-19 | 2016-11-30 | 出光兴产株式会社 | 新型化合物 |
CN105542793A (zh) * | 2016-02-26 | 2016-05-04 | 山西大学 | 一种手性室温离子液晶化合物及其制备方法 |
CN105623673A (zh) * | 2016-02-26 | 2016-06-01 | 山西大学 | 一种含多酸的手性液晶复合物及其制备方法 |
CN107162869A (zh) * | 2017-05-05 | 2017-09-15 | 吉林奥来德光电材料股份有限公司 | 芘类衍生物有机电致发光材料及其制备方法和有机电致发光器件 |
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