CN114605452B - 一种具有聚集诱导发光、大斯托克斯位移荧光染料氟硼化合物及其制备方法 - Google Patents
一种具有聚集诱导发光、大斯托克斯位移荧光染料氟硼化合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有聚集诱导发光、大斯托克斯位移荧光染料氟硼化合物及其制备方法,其结构为β‑二羰基氟硼化合物,具有良好热稳定性。该方法是将1,3‑二(4‑溴苯基)‑3‑羟丙烯基‑酮(化合物1)和具有螺旋桨取代基的苯胺(或咔唑衍生物2)反应得到中间体,进一步与三氟化硼乙醚试剂反应得到相应的氟硼化合物,即β‑二羰基氟硼化合物。本发明制得的氟硼化合物具有聚集诱导发光性能,荧光最大发射峰可达654 nm,斯托克斯位移达127 nm,质量损失5%时的温度达440.9℃。
Description
技术领域
本发明属于荧光小分子材料领域,涉及一种具有聚集诱导发光、大斯托克斯位移荧光染料氟硼化合物及其制备方法。
背景技术
β-二羰基氟硼络合物由于具有荧光量子产率高、摩尔吸光系数大、双光子吸收截面大和室温磷光等优点受到人们的关注,是一类常见的有机荧光染料,已被广泛应用在荧光成像、生物标记、医药、环境等领域。但是由于其发射波长较短、聚集诱导荧光淬灭、热稳定性差及斯托克斯位移较小(<50纳米)等不足,限制了它们在荧光标记、荧光探针、光动力治疗、捕光系统、激光染料、晶体管场效应、生物成像、有机发光二极管等领域的应用,成为β-二羰基氟硼络合物的发展瓶颈。
聚集诱导发光(Aggregation-induced emission,AIE)材料可克服传统荧光分子的聚集诱导荧光淬灭现象。此外,电子供体—受体(D-A)型氟硼络合物通过分子内的电荷转移作用以实现发射红移和增大斯托克斯位移的目的。然而,如何制备具有聚集诱导发光、大斯托克斯位移和优异热稳定性的氟硼络合物荧光染料是一个关键问题,目前还没有文献或专利报道这一类的氟硼络合物及其制备方法。
发明内容
本发明的目的是针对现有氟硼化合物易发生聚集诱导荧光淬灭、斯托克斯位移小和热稳定性差的不足,提供一种具有聚集诱导发光、大斯托克斯位移和优异热稳定性的荧光染料氟硼化合物及其制备方法。其结构式如下:
其中,R1为如下取代的苯胺基或咔唑基,其结构如下:
R2为-(CH2)nCH3(n=0-30)的直链烷基。
本发明中的氟硼化合物拥有螺旋桨结构的咔唑或苯胺取代基AIE单元可有效地抑制分子间的聚集,有利于分子具有聚集诱导发光性能。同时,富电子的苯胺或咔唑取代基可与缺电子的六元氟硼环形成电子推拉体系,有利于荧光发射红移和斯托克斯位移增加。通过调控分子中电子推拉效应的强弱提高氟硼化合物的热稳定性。
当本发明中氟硼化合物R1的取代基为咔唑基时,在其3,6位引入1个或2个大位阻的取代基起到抑制氟硼化合物π-π聚集作用,R2直链取代烷基可增加氟硼化合物在不同溶剂中的溶解性,其碳链长短不影响氟硼化合物的光物理性能。
另外,本发明还提供上述的聚集诱导发光、大斯托克斯位移、热稳定性优异的氟硼化合物的制备方法,路线如下:
R1为如下取代的苯胺基或咔唑基,其结构如下:
R2为-(CH2)nCH3(n=0-30)的直链烷基。
包括如下步骤:
(1)1,3-二(4-溴苯基)-3-羟丙烯基-酮(化合物1)和2倍摩尔量的取代基的苯胺(或咔唑衍生物2)加到碱性水溶液中,通惰性气体10~20min,再加入以化合物1计摩尔百分数为1%~10%钯试剂和摩尔百分数为3%~60%膦配体,在惰性气体保护下加热回流反应12~72h,旋蒸除去溶剂,柱层析得到化合物3;优选钯催化剂为Pd(PPh3)4、Pd(OAc)2、Pd(PPh2)Cl2或Pd(dppf)Cl2,碱性水溶液包括Na2CO3水溶液、Cs2CO3水溶液、K2CO3水溶液、KOH水溶液、氨水或NaOH水溶液,膦配体包括碳膦配体、氧膦配体和氮膦配体。
(2)将化合物3溶解于干燥的二氯甲烷,在氮气条件下将以化合物3计5-20倍当量的三氟化硼乙醚加入到上述溶液中,回流条件下搅拌2-6小时,旋去溶剂后,柱层析得到氟硼化合物(BF)。
相对于现有技术,本发明具有如下优点:
(1)本发明制备的氟硼化合物的聚集诱导发光材料,其斯托克斯位移达到127nm,有利于提高该类材料的检测灵敏度和准确度、降低荧光自淬灭和增加生物成像的信噪比。
(2)选用不同给电子能力和空间位阻的咔唑或苯胺转子单元可以方便地调节氟硼化合物的斯托克斯位移、荧光发射和荧光量子产率等光物理性质。
(3)本发明路线制备聚集诱导发光氟硼化合物,质量损失5%时的温度达440.9℃,具有热稳定性好的特点。
附图说明
图1为实施例1制备的BF1在THF-水混合溶剂中的荧光谱图。
图2为实施例1制备的BF1在THF-水混合溶剂中的荧光强度与水含量关系图。
图3为实施例2制备的BF2在THF-水混合溶剂中的荧光谱图。
图4为实施例2制备的BF2在THF-水混合溶剂中的荧光强度与水含量关系图。
图5为实施例1-3制备的BF1、BF2和BF3的热重曲线。
具体实施方式
下面结合实施例对本发明的具体实施作进一步说明,但本发明要求保护的范围并不局限于实施例表述的范围。以下括号的百分比无特别说明均为产率。
实施例1
BF1的制备
化合物1-1根据文献F Song,G Wei,X Jiang,F Li,C Zhu,Y Cheng,Chem.Commun.,2013,49,5772-5774合成。
化合物2-1根据文献W Qin,K Li,G Feng,M Li,Z Yang,B Liu B Tang,Adv.Funct.Mater.,2014,24,635-643合成。
(1)化合物3-1的制备
碳酸铯(30mmol)、化合物1-1(10mmol)、化合物2-1(20mmol)、叔丁基膦配体(2.0mmol)、80mL水和80mL甲苯混合后,通入Ar气保护后加入醋酸钯(0.4mmol),加热至90℃,反应12h。结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到6.22g黄色固体,产率56%。1H NMR(400MHz,CDCl3)δ:16.47(s,1H),7.77(br,3H),7.19-6.99(m,35H),6.96-6.81(m,16H),6.64(s,1H),3.82(s,6H)。
(2)化合物BF1的制备
化合物3-1(0.5mmol)溶于20mL二氯甲烷,在氮气氛围下将BF3.Et2O(5mmol)加入到上述溶液中,加热回流2小时,结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到0.53g红色固体,产率90%。1H NMR(400MHz,CDCl3)δ:7.88(br,4H),7.18-7.01(m,34H),7.00-6.95(m,4H),6.92-6.82(m,13H),3.83(s,6H)。
实施例2
BF2的制备
化合物2-2根据P Chen,J Wang,L Niu,Y Chen,Q Yang,J.Mater.Chem.C,2017,5,12538-12546合成。
(1)化合物3-2的制备
叔丁醇钠(40mmol)、化合物1-1(10mmol)、化合物2-2(20mmol)、(t-BuP)3HF4膦配体(2.5mmol)、100mL甲苯混合后,通入Ar气保护后加入醋酸钯(0.5mmol),加热至100℃,反应18h。结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到5.31g黄色固体,产率50%。1HNMR(400MHz,CDCl3)δ:16.47(s,1H),8.73(d,2H),8.33(dd,2H),7.97(m,2H),7.91-7.24(m,46H),5.35(s,1H)。
(2)化合物BF2的制备
化合物3-2(0.5mmol)溶于20mL二氯甲烷,在氮气氛围下将BF3.Et2O(6mmol)加入到上述溶液中,加热回流3小时,结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到0.51g红色固体,产率92%。1H NMR(400MHz,CDCl3)δ:8.74(d,2H),8.35(dd,2H),7.98(m,2H),7.92-7.24(m,46H),5.45(s,1H)。
实施例3
BF3的制备
化合物2-3根据Y Shi,K Hou,Y Wang,K Wang,H Ren,Pang,M;Chen,F;S.Zhang,J.Mater.Chem.A 2016,4,5415-5422合成。
(1)化合物3-3的制备
叔丁醇钠(40mmol)、化合物1-1(10mmol)、化合物2-3(20mmol)、(t-BuP)3HF4膦配体(1.2mmol)、100mL甲苯混合后,通入Ar气保护后加入醋酸钯(0.3mmol),加热至90℃,反应15h。结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到4.84g黄色固体,产率48%。1HNMR(400MHz,CDCl3)δ:16.48(s,1H),8.35(d,2H),8.01(m,3H),7.83(d,2H),7.70-7.19(m,23H),6.82(d,8H),6.02(s,1H),3.89(s,12H)。
(2)化合物BF3的制备
化合物3-3(0.5mmol)溶于20mL二氯甲烷,在氮气氛围下将BF3.Et2O(7mmol)加入到上述溶液中,加热回流4小时,结束反应,旋蒸除去溶剂,粗产物经过柱层析纯化,得到0.46g红色固体,产率88%。1H NMR(400MHz,CDCl3)δ:8.36(d,2H),8.01(m,3H),7.87(d,2H),7.74-7.19(m,23H),6.83(d,8H),6.02(s,1H),3.90(s,12H)。
性能测试例
BF1在THF-水混合溶剂中荧光谱图和荧光强度与水含量关系图如图1和图2所示,随着不良溶剂水含量的增加,荧光强度表现出聚集诱导荧光增强的现象。
BF2在THF-水混合溶剂中荧光谱图和荧光强度与水含量关系图如图3和图4所示,随着不良溶剂水含量的增加,荧光强度表现出聚集诱导荧光增强的现象。
BF1、BF2和BF3的热重曲线如图5所示,质量损失5%时的温度分别为440.9、416.3和423.2℃,表明氟硼络合物具有优异的热稳定性。
BF1和BF2在不同溶剂中的光物理性能数据如表1和表2所示,BF1在氯仿中的斯托克斯位移为127nm,BF2在甲苯中的斯托克斯位移为108nm。
表1 BF1在不同溶剂中的光物理性能数据
表2 BF2在不同溶剂中的光物理性能数据
Claims (5)
1.一种具有聚集诱导发光、大斯托克斯位移荧光染料氟硼化合物,其特征在于结构式为:
其中R1的结构为:
2.一种权利要求1所述的氟硼化合物的制备方法,其特征在于包括如下步骤:
(1)1,3-二(4-溴苯基)-3-羟丙烯基-酮和2倍摩尔量的加到碱性水溶液中,通惰性气体10~20min,再加入以1,3-二(4-溴苯基)-3-羟丙烯基-酮计量摩尔百分数为1%~10%钯试剂和摩尔百分数为3%~60%膦配体,在惰性气体保护下加热回流反应12~72h,旋蒸去溶剂,柱层析得到中间体
(2)中间体溶解于干燥的二氯甲烷,在氮气条件下将以中间体计5-20倍摩尔当量的三氟化硼乙醚加入到上述溶液中,回流条件下搅拌2-6小时,除去溶剂后,柱层析得到氟硼化合物
3.根据权利要求2所述氟硼化合物的制备方法,在步骤(1)中所述钯试剂为:Pd(dppf)Cl2、Pd(PPh3)4。
4.根据权利要求2所述氟硼化合物的制备方法,在步骤(1)中所述碱性水溶液选自Na2CO3水溶液、Cs2CO3水溶液、K2CO3水溶液、KOH水溶液、氨水或NaOH水溶液。
5.根据权利要求2所述氟硼化合物的制备方法,在步骤(1)中所述膦配体选自碳膦配体、氧膦配体和氮膦配体。
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