CN111233681B - 一种星状四胺芘化合物、制备方法及其应用 - Google Patents
一种星状四胺芘化合物、制备方法及其应用 Download PDFInfo
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 title claims abstract description 82
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- PLNCGRLKUTXAOL-UHFFFAOYSA-N n,n-bis(4-methoxyphenyl)-4-phenylaniline Chemical group C1=CC(OC)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC=CC=1)C1=CC=C(OC)C=C1 PLNCGRLKUTXAOL-UHFFFAOYSA-N 0.000 description 1
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- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
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Abstract
本发明涉及一种星状四胺芘化合物、制备方法及其应用,属于热致变色发光材料技术领域,解决了现有技术中荧光材料温度检测中量子产率低的问题。一种星状四胺芘化合物,分子式为C120H94N4O8;星状四胺芘化合物的制备方法包括:步骤1:制备(4’‑(双(4‑甲氧基苯基)氨基)‑(1,1’‑联苯基)‑4‑基)硼酸;步骤2:制备星状四胺芘化合物。星状四胺芘化合物应用于荧光温度检测。本发明中的星状四胺芘化合物具有高量子产率,温度响应具有宽泛的检测范围以及高的灵敏度和准确性,可作为良好的荧光温度计。
Description
技术领域
本发明涉及热致变色发光材料技术领域,尤其涉及一种星状四胺芘化合物、制备方法及其应用。
背景技术
温度是一个非常关键的基本物理量,与科学技术的各个领域都密切相关,开发准确可靠的温度传感器十分重要。荧光温度计由于具有低成本,响应速度快,灵敏度高等优点而具有很大的发展前景。目前已报道的荧光温度计包括有机染料,聚合物,金属配合物,金属有机框架和纳米材料等。现有的温度传感器一般基于发射强度的变化,且在高温情况下,非辐射跃迁增加,发光较弱。为了提高荧光温度计的准确度,研究基于波长变化的,在高温条件下具有高量子产率的荧光温度计是很有意义的。
分子内电荷转移是发生在分子内部给受体之间的电子转移反应,近年来在光功能材料,光学传感器,分子器件等方面有着广泛应用。分子内电荷转移激发态的发光对环境非常敏感,例如溶剂,温度,粘度等因素,因此可以通过控制激发态的性质来调节发射波长和强度。分子内电荷转移分子是作为荧光温度计的一种有效材料。
2011年,Shayu Li,Yi Li和Guoqiang Yang等人报道了一种新型三芳基硼荧光温度计(DPTB),该分子通过温度调控LE态(local excited state)和TICT(intramolecularcharge transfer)激发态之间的平衡,MOE(二乙二醇二甲醚)溶液在-50~+100℃之间表现出温度依赖的荧光现象。随着温度的升高,发射波长蓝移,发射波长和温度之间表现出良好的线性关系,可用作荧光温度计,且该温度计拥有较好的稳定性和可逆性。
发明内容
鉴于上述的分析,本发明实施例旨在提供一种星状四胺芘化合物、制备方法及其应用,用以解决现有荧光材料温度检测中量子产率低的问题。
本发明是通过以下技术方案实现的:
一种星状四胺芘化合物,分子式为C120H94N4O8,结构式为:
一种星状四胺芘化合物的制备方法,包括如下步骤:
步骤1:制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
步骤2:制备星状四胺芘化合物。
进一步,步骤1为在惰性气氛下,正丁基锂的作用下,4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺与硼酸酯反应,经盐酸酸化制得(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸。
进一步,步骤2为在惰性气氛下,碳酸钾和四(三苯基膦)钯催化剂的作用下,(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸与1,3,6,8-四溴芘反应得星状四胺芘化合物。
进一步,步骤1中反应条件为-70℃~-90℃下加入正丁基锂保持1~2h后加入硼酸酯,升温至20~30℃温度下保持1~2h,最后加入盐酸酸化;4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺、硼酸酯与正丁基锂的摩尔比为1∶(1.1~2)∶(1~2)。
进一步,步骤2中反应溶剂为四氢呋喃与水的混合溶剂;四氢呋喃与水体积比为1∶1~4∶1;反应的时间为24~72h;(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸、1,3,6,8-四溴芘、碳酸钾、四(三苯基膦)钯的摩尔比为(4.2~6)∶1∶(10~20)∶(0.02~0.1)。
进一步,步骤1中反应的溶剂为四氢呋喃;硼酸酯为硼酸三甲酯、硼酸三异丙酯、异丙醇频哪醇硼酸酯中任意一种。
一种星状四胺芘化合物的应用于荧光温度检测。
进一步,在乙醚溶剂中,170~300K温度下,其发射波长与温度呈线性关系。
进一步,在乙二醇二甲醚溶剂中,240~400K温度下,其发射波长与温度呈现线性关系。
与现有技术相比,本发明至少可实现如下有益效果之一:
本发明合成的星状四胺芘化合物,溶液的发光可以通过溶剂极性调控实现从蓝光到红光的发射,具有明显的溶剂效应。不同溶剂中的溶液发光均具有明显的温度依赖性,在乙醚溶剂中,在170~300K随温度降低可以实现蓝光到橙红色光的发射,在二乙二醇二甲醚中,在240~400K随温度的升高可以实现橙红色光到绿光的发射。在这两种溶剂中,发光波长与温度均呈现出良好的线性关系,可用于温度检测,且具有较宽的检测范围,较高的灵敏度,准确性及良好的稳定性和可逆性。星状四胺芘化合物具有较高的量子产率,有利于其在发光领域的应用。
本发明中,上述各技术方案之间还可以相互组合,以实现更多的优选组合方案。本发明的其他特征和优点将在随后的说明书中阐述,并且,部分优点可从说明书中变得显而易见,或者通过实施本发明而了解。本发明的目的和其他优点可通过说明书以及附图中所特别指出的内容中来实现和获得。
附图说明
附图仅用于示出具体实施例的目的,而并不认为是对本发明的限制,在整个附图中,相同的参考符号表示相同的部件。
图1为式I所示星状四胺芘化合物在不同溶剂中荧光发射光谱变化图(1×10-5mol/L);
图2为式I所示星状四胺芘化合物在乙醚中,300~170K范围内不同温度下的荧光发射光谱变化图(1×10-5mol/L);
图3为式I所示星状四胺芘化合物在二乙二醇二甲醚中,240~400K范围内不同温度下的荧光发射光谱变化图(1×10-5mol/L);
图4为式I所示星状四胺芘化合物在乙醚中,300~170K范围内不同温度下最大发射波长与温度的关系图;
图5为式I所示星状四胺芘化合物在二乙二醇二甲醚中,240~400K范围内不同温度下最大发射波长与温度的关系图;
图6为式I所示星状四胺芘化合物在二乙二醇二甲醚中最大发射波长在240K和400K变化的循环图;
图7为星状四胺芘化合物结构式图;
图8为式I所示星状四胺芘化合物在乙酸乙酯中,300~180K范围内不同温度下的荧光发射光谱变化图(1×10-5mol/L);
图9为式I所示星状四胺芘化合物在四氢呋喃中,300~180K范围内不同温度下的荧光发射光谱变化图(1×10-5mol/L);
图10为式I所示星状四胺芘化合物在二氯甲烷中,300~190K范围内不同温度下的荧光发射光谱变化图(1×10-5mol/L);
图11为式I所示星状四胺芘化合物在乙酸乙酯,四氢呋喃和二氯甲烷中,不同温度下最大发射波长与温度的关系图。
具体实施方式
下面结合附图来具体描述本发明的优选实施例,其中,附图构成本申请一部分,并与本发明的实施例一起用于阐释本发明的原理,并非用于限定本发明的范围。
本发明提供一种星状四胺芘化合物,星状四胺芘化合物是以芘为中心,连接有四个4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)基团,具有星状分子结构的化合物,其结构如式I所示:
本发明提供一种星状四胺芘化合物制备方法,包含以下步骤:
步骤1:制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
在惰性气氛下,4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺在低温下与正丁基锂发生卤素-锂交换反应形成芳基锂,芳基锂与硼酸酯发生亲核取代反应形成芳基硼酸酯,经盐酸进一步酸化水解即得式Ⅱ所示(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸。反应方程式参见下反应式(1-1)。
其中,4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺可按照现有方法进行制备,参见文献中记载的方法:Y.J.Chang,T.J.Chow.Triaryl linked donor acceptordyads for high-performance dye-sensitized solar cells[J].Tetrahedron 2009,65:9626–9632.
步骤2:制备星状四胺芘化合物;
星状四胺芘化合物通过Suzuki偶联反应制备得到。
惰性气氛下,在碳酸钾存在下,四(三苯基膦)钯催化下,式Ⅱ所示(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸与商业购置的1,3,6,8-四溴芘发生交叉偶联反应即得式I所示星状四胺芘化合。反应方程式参见下反应式(1-2)。
催化循环过程首先是四(三苯基膦)钯与1,3,6,8-四溴芘发生氧化加成反应生成二价钯的络合物,然后与(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸在碳酸钾作用下发生金属转移反应,最后进行还原反应生成星状四胺芘化合物。
具体的,步骤1中:
反应的溶剂为四氢呋喃、甲苯,正己烷、乙醚等非极性的溶剂,优选为四氢呋喃溶剂;
所用硼酸酯为常规硼酸酯,硼酸三甲酯,硼酸三异丙酯,异丙醇频哪醇硼酸酯中任意一种;
反应温度与时间为:-70℃~-90℃下加入正丁基锂保持1~2h,加入硼酸酯升温至20~30℃保持1~2h,最后加入过量盐酸酸化。
随着盐酸的加入,反应体系中先生成(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸沉淀,继续滴加过量盐酸至(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸沉淀消失,稀盐酸浓度为1-3mol/L。4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺、硼酸酯与所述正丁基锂的摩尔比为1∶1.1~2∶1~2;反应结束后,采用柱层析分离提纯,洗脱剂为二氯甲烷与甲醇的混合液,二氯甲烷与甲醇体积比为50∶1。
具体的,步骤2中:
反应溶剂为四氢呋喃、甲苯,正己烷、乙醚等非极性物质与水混合溶剂,其体积比均为1∶1~4∶1;
反应在回流状态下进行,反应的时间为24~72h;
(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸、1,3,6,8-四溴芘、碳酸钾、四(三苯基膦)钯的摩尔比为(4.2~6)∶1∶(10~40)∶(0.02~0.1);
反应结束后,采用柱层析分离提纯,洗脱剂可为石油醚和二氯甲烷的混合液,石油醚和二氯甲烷体积比为1∶2。
实施例1
本实施例提供了一种星状四胺芘化合物制备方法,包含以下步骤:
(1)制备4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺;
4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺的合成参照反应式(1-3),合成方法参照文献Y.J.Chang,T.J.Chow.Triaryl linked donor acceptor dyads forhigh-performance dye-sensitized solar cells[J].Tetrahedron 2009,65:9626–9632.
(2)制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
将4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺(1012mg/2.2mmol)溶解在15mL四氢呋喃溶剂中,在氮气保护下降温至-78℃,用注射器缓慢加入浓度为2.5mol/L的正丁基锂正己烷溶液(1.5mL/3.75mmol),混合溶液在-78℃下搅拌1h,继续加入硼酸三甲酯(364mg/3.5mmol),搅拌2h后升温至25℃继续反应1h,加入浓度为5%过量盐酸至硼酸沉淀消失。将反应体系用二氯甲烷萃取,有机相用无水硫酸钠干燥并通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:二氯甲烷/甲醇50/1,v/v)获得760mg浅黄绿色(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸固体,产率:81%。
氢谱结果为:1H NMR(400MHz,DMSO-d6)δ8.04(s,2H),7.80(d,J=8.4Hz,2H),7.53(dd,J=15.0,8.3Hz,4H),7.03(d,J=8.9Hz,4H),6.91(d,J=8.9Hz,4H),6.81(d,J=8.7Hz,2H),3.73(s,6H).ESI-MS calcd for C26H23BNO4[M-H]+:424.2.Found:424.3.
(3)制备星状四胺芘化合物;
将(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸(757mg/1.78mmol),1,3,6,8-四溴芘(192mg/0.37mmol),四三苯基膦钯(32mg/0.028mmol),2mol/L碳酸钾水溶液7mL,四氢呋喃18mL混合于反应瓶中,在氮气保护下,加热搅拌至90℃回流反应24h。反应完成后,降至室温,有机相用二氯甲烷萃取并用无水硫酸钠干燥,通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:石油醚/二氯甲烷1/1,v/v)获得555mg黄绿色星状四胺芘化合物固体,制备得到的星状四胺芘化合物的分子式为C120H94N4O8。产率:87%。
氢谱结果为:1H NMR(400MHz,CDCl3)δ8.28(s,4H),8.09(s,2H),7.73(s,16H),7.53(d,J=8.6Hz,8H),7.12(d,J=8.9Hz,16H),7.04(d,J=8.6Hz,8H),6.86(d,J=9.0Hz,16H),3.82(s,24H).MALDI-HRMS calcd for C120H94N4O8[M]+:1719.71499.Found:1719.70936.
(4)星状四胺芘化合物溶液条件下光学性质测试;
星状四胺芘化合物在不同溶剂中(c=1×10-5mol/L)荧光发射光谱如图1所示,波长与强度受到溶剂极性的强烈影响,表明这是典型的由给受体结构而产生的分子内电荷转移态的发光,随着溶剂极性增大,发射波长由472nm红移至624nm,150nm左右的波长红移使溶液可以实现从蓝光到橙红色发光的调控。星状四胺芘化合物在不同溶剂中都有较高的量子产率,其中在甲苯,1,4-二氧六环,乙醚和氯苯中的量子产率均在90%以上。
星状四胺芘化合物在乙醚中的发光表现出强烈的温度依赖性。当温度从300K逐渐降至170K时,发射光谱(c=1×10-5mol/L),如图2所示,发射波长从491nm的青色发光逐渐红移,伴随着发光强度的下降,在170K时,变为596nm的橙色发光。温度强烈影响了分子电荷转移激发态的构型,当温度下降时,分子激发态的构型更加平面化,共轭程度更好,导致发光更加红移。
星状四胺芘化合物在高沸点(159.7℃)溶剂二乙二醇二甲醚中(c=1×10-5mol/L),同样表现出强烈的温度依赖性,发射光谱如图3所示。当温度从240K逐渐增加至400K时,由于温度对构型的影响,发射波长由568nm蓝移至495nm,发光强度增大。同时,其在四氢呋喃,二氯甲烷和乙酸乙酯中(c=1×10-5mol/L),发射波长都随温度下降发生红移。
在300~170K范围内不同温度下星状四胺芘化合物在乙醚中的最大发射波长与温度的关系图如图4所示,发射波长与温度呈现出良好的线性关系,拟合函数方程为λ=728.74-0.80T,相关系数为0.9965,发射波长与温度之间良好的线性关系说明该体系可以实现温度的定量检测,对应的每摄氏度波长变化高达0.80nm,说明该发光温度计具有很高的灵敏度和准确性。
同时,在240~400K范围内不同温度下星状四胺芘化合物在二乙二醇二甲醚中的最大发射波长与温度的关系图如图5所示,发射波长与温度的拟合函数方程为λ=760.42-0.65T,相关系数为0.9915,同样呈现出良好的线性关系,对应的每摄氏度波长变化为0.65nm,表明该分子在高温条件时,也可以用作发光温度计并且性能良好。
将星状四胺芘在二乙二醇二甲醚中的发光在240K和400K温度下循环测试了多次,没有观察到明显的波长和强度变化,如图6所示,表明该分子具有良好的稳定性,且该荧光温度计具有良好的可逆性。
实施例2
本实施例提供了一种星状四胺芘化合物制备方法,包含以下步骤:
(1)制备4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺;
具体制备方法参见实施例1。
(2)制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
将4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺(459mg/1mmol)溶解在6mL四氢呋喃溶剂中,在氮气保护下降温至-80℃,用注射器缓慢加入浓度为2.5mol/L的正丁基锂正己烷溶液(0.6mL/1.5mmol),混合溶液在-80℃下搅拌1h,继续加入硼酸三甲酯(156mg/1.5mmol),搅拌2h后恢复升温至25℃室温继续反应1h,加入浓度为5%过量盐酸至硼酸沉淀消失。将反应体系用二氯甲烷萃取,有机相用无水硫酸钠干燥并通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:二氯甲烷/甲醇50/1,v/v)获得320mg浅黄绿色(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸固体,产率:75%。
(3)制备星状四胺芘化合物;
将(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸(255mg/0.6mmol),1,3,6,8-四溴芘(52mg/0.1mmol),四三苯基膦钯(11mg/0.0095mmol),2mol/L碳酸钾水溶液1mL,四氢呋喃4mL混合于反应瓶中,在氮气保护下,加热搅拌至90℃回流反应24h。反应完成后,降至室温,有机相用二氯甲烷萃取并用无水硫酸钠干燥,通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:石油醚/二氯甲烷1/1,v/v)获得134mg黄绿色星状四胺芘化合物固体,制备得到的星状四胺芘化合物的分子式为C120H94N4O8。产率:78%
(4)星状四胺芘化合物在乙酸乙酯中的光学性质测试;
如图8所示,在乙酸乙酯中,当温度从300K降到180K时,发射波长从528nm红移至611nm,波长与温度的线性拟合方程为λ=735.44-0.69T,相关系数为0.9969。
实施例3
本实施例提供了一种星状四胺芘化合物制备方法,包含以下步骤:
(1)制备4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺;
具体制备方法参见实施例1。
(2)制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
将4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺(1381mg/3mmol)溶解在20mL四氢呋喃溶剂中,在氮气保护下降温至-78℃,用注射器缓慢加入浓度为2.5mol/L的正丁基锂正己烷溶液(1.4mL/3.5mmol),混合溶液在-78℃下搅拌1h,继续加入硼酸三甲酯(374mg/3.6mmol),搅拌2h后恢复升温至25℃室温继续反应1h,加入浓度为5%过量盐酸至硼酸沉淀消失。将反应体系用二氯甲烷萃取,有机相用无水硫酸钠干燥并通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:二氯甲烷/甲醇50/1,v/v)获得1050mg浅黄绿色(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸固体,产率:82%。
(3)制备星状四胺芘化合物;
将(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸(936mg/2.2mmol),1,3,6,8-四溴芘(259mg/0.5mmol),四三苯基膦钯(23mg/0.02mmol),2mol/L碳酸钾水溶液8mL,四氢呋喃20mL混合于反应瓶中,在氮气保护下,加热搅拌至90℃回流反应24h。反应完成后,降至室温,有机相用二氯甲烷萃取并用无水硫酸钠干燥,通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:石油醚/二氯甲烷1/1,v/v)获得620mg黄绿色星状四胺芘化合物固体,制备得到的星状四胺芘化合物的分子式为C120H94N4O8。产率:72%。
(4)星状四胺芘化合物在四氢呋喃中的光学性质测试;
如图9所示,在四氢呋喃中,当温度从300K降到180K时,发射波长从542nm红移至627nm,波长与温度的线性拟合方程为λ=753.32-0.71T,相关系数为0.9984;
实施例4
本实施例提供了一种星状四胺芘化合物制备方法,包含以下步骤:
(1)制备4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺;
具体制备方法参见实施例1。
(2)制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
将4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺(690mg/1.5mmol)溶解在10mL四氢呋喃溶剂中,在氮气保护下降温至-78℃,用注射器缓慢加入浓度为2.5mol/L的正丁基锂正己烷溶液(1.2mL/2.1mmol),混合溶液在-78℃下搅拌1h,继续加入硼酸三甲酯(208mg/2mmol),搅拌2h后恢复升温至25℃室温继续反应1h,加入浓度为5%过量盐酸至硼酸沉淀消失。将反应体系用二氯甲烷萃取,有机相用无水硫酸钠干燥并通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:二氯甲烷/甲醇50/1,v/v)获得490mg浅黄绿色(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸固体,产率:77%。
(3)制备星状四胺芘化合物;
将(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸(468mg/1.1mmol),1,3,6,8-四溴芘(104mg/0.2mmol),四三苯基膦钯(14mg/0.012mmol),2mol/L碳酸钾水溶液2mL,四氢呋喃6mL混合于反应瓶中,在氮气保护下,加热搅拌至90℃回流反应24h。反应完成后,降至室温,有机相用二氯甲烷萃取并用无水硫酸钠干燥,通过减压旋蒸除去溶剂,柱层析分离提纯(洗脱剂:石油醚/二氯甲烷1/1,v/v)获得258mg黄绿色星状四胺芘化合物固体,制备得到的星状四胺芘化合物的分子式为C120H94N4O8。产率:75%。
(4)星状四胺芘化合物在二氯甲烷中的光学性质测试;
如图10所示,在二氯甲烷中,当温度从300K降到190K时,发射波长从564nm红移至646nm,波长与温度的线性拟合方程为λ=784.07-0.73T,相关系数为0.9992。
星状四胺芘化合物在乙酸乙酯,四氢呋喃和二氯甲烷中的发光同样表现出明显的温度依赖性,随温度变化的荧光发射光谱图如图8,图9,图10所示。随着温度的降低,发射波长都有明显的红移且发光强度减小,同时,最大发射波长均与温度呈现出良好的线性关系,如图11所示。
本实施例还提供了一种星状四胺芘化合物在荧光温度检测中的应用,溶液的发光可以通过溶剂极性调控从蓝光到红光的发射;不同溶剂中的溶液发光均具有明显的温度依赖性,可用于温度检测。所述星状四胺芘化合物具有较高的量子产率,且温度响应具有较宽的检测范围,较高的灵敏度,准确性及良好的稳定性和可逆性,可以作为良好的荧光温度计。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
2.一种星状四胺芘化合物的制备方法,用于制备权利要求1所述的星状四胺芘化合物,其特征在于,包括如下步骤:
步骤1:制备(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸;
步骤2:制备星状四胺芘化合物。
3.根据权利要求2所述的星状四胺芘化合物的制备方法,其特征在于,所述步骤1为在惰性气氛下,正丁基锂的作用下,4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺与硼酸酯反应,经盐酸酸化制得(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸。
4.根据权利要求2所述的星状四胺芘化合物的制备方法,其特征在于,所述步骤2为在惰性气氛下,碳酸钾和四(三苯基膦)钯催化剂的作用下,(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸与1,3,6,8-四溴芘反应得星状四胺芘化合物。
5.根据权利要求3所述的星状四胺芘化合物的制备方法,其特征在于,所述步骤1中反应条件为-70℃~-90℃下加入正丁基锂保持1~2h后加入硼酸酯,升温至20~30℃温度下保持1~2h,最后加入盐酸酸化;4’-溴-N,N-双(4-甲氧基苯基)-(1,1’-联苯基)-4-胺、硼酸酯与正丁基锂的摩尔比为1∶(1.1~2)∶(1~2)。
6.根据权利要求4所述的星状四胺芘化合物的制备方法,其特征在于,所述步骤2中反应溶剂为四氢呋喃与水的混合溶剂;四氢呋喃与水体积比为1∶1~4∶1;反应的时间为24~72h;(4’-(双(4-甲氧基苯基)氨基)-(1,1’-联苯基)-4-基)硼酸、1,3,6,8-四溴芘、碳酸钾、四(三苯基膦)钯的摩尔比为(4.2~6)∶1∶(10~20)∶(0.02~0.1)。
7.根据权利要求5所述的星状四胺芘化合物的制备方法,其特征在于,所述步骤1中反应的溶剂为四氢呋喃;硼酸酯为硼酸三甲酯、硼酸三异丙酯、异丙醇频哪醇硼酸酯中任意一种。
8.一种星状四胺芘化合物的应用,其特征在于,权利要求1所述的星状四胺芘化合物或权利要求2-7任一项所述的制备方法得到的星状四胺芘化合物用于荧光温度检测。
9.根据权利要求8所述的星状四胺芘化合物的应用,其特征在于,在乙醚溶剂中,170~300K温度下,其发射波长与温度呈线性关系。
10.根据权利要求8或9所述的星状四胺芘化合物的应用,其特征在于,在乙二醇二甲醚溶剂中,240~400K温度下,其发射波长与温度呈现线性关系。
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